Method of manufacturing semiconductor device, method of processing substrate substrate processing apparatus and non-transitory computer-readable recording medium

ABSTRACT

An insulating film including characteristics such as low permittivity, a low etching rate and a high insulation property is formed. Supplying a gas containing an element, a carbon-containing gas and a nitrogen-containing gas to a heated substrate in a processing vessel to form a carbonitride layer including the element, and supplying the gas containing the element and an oxygen-containing gas to the heated substrate in the processing vessel to form an oxide layer including the element are alternately repeated to form on the substrate an oxycarbonitride film having the carbonitride layer and the oxide layer alternately stacked therein.

CROSS-REFERENCE TO RELATED PATENT APPLICATION

This U.S. non-provisional patent application claims priority under 35U.S.C. §119 of Japanese Patent Applications No. 2011-005638 filed onJan. 14, 2011 and No. 2011-268002 filed on Dec. 7, 2011, in the JapanesePatent Office, the entire contents of which are hereby incorporated byreference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method of manufacturing asemiconductor device including a process of forming a thin film on asubstrate, a method of processing a substrate and a substrate processingapparatus.

2. Description of the Related Art

A process of manufacturing a semiconductor device includes a process offorming a silicon insulating film such as a silicon oxide film (a SiO₂film, hereinafter referred to as a SiO film) or a silicon nitride film(a Si₃N₄ film, hereinafter referred to as a SiN film) on a wafer such asa silicon wafer. Since the silicon oxide film has a good insulatingproperty, low permittivity, etc., the silicon oxide film is widely usedas an insulating film or an interlayer film. In addition, since thesilicon nitride film is good in insulating property, corrosionresistance, permittivity, film stress controllability, etc., the siliconnitride film is widely used as an insulating film, a mask film, a chargeaccumulation film, or a stress control film. Further, a technique ofadding carbon (C) to these insulating films is already known (forexample, see Patent Document 1), and thus, etching resistance of theinsulating film can be improved.

PRIOR ART DOCUMENT

[Patent Document 1] Japanese Patent Laid-open Publication No.2005-268699

SUMMARY OF THE INVENTION

When carbon is added to insulating films, the etching resistance of theinsulating films is improved, but permittivity is increased and leakresistance is deteriorated. That is, each of the insulating films hasadvantages and defects, but in the related art, there is no film havingcharacteristics such as low permittivity, a low etching rate, and a highinsulating property.

Accordingly, it is an aspect of the present invention to provide amethod of manufacturing a semiconductor device, a method of processing asubstrate and a substrate processing apparatus capable of forming aninsulating film having low permittivity, a low etching rate, and a highinsulating property.

According to one aspect, there is provided a method of manufacturing asemiconductor device, including: (a) supplying a gas containing anelement, a carbon-containing gas and a nitrogen-containing gas to aheated substrate in a processing vessel to form a carbonitride layerincluding the element; (b) supplying the gas containing the element andan oxygen-containing gas to the heated substrate in the processingvessel to form an oxide layer including the element; and (c) alternatelyrepeating the steps (a) and (b) to form on the substrate anoxycarbonitride film having the carbonitride layer and the oxide layeralternately stacked therein.

According to another embodiment of the present invention, there isprovided a method of processing a substrate, including: (a) supplying agas containing an element, a carbon-containing gas and anitrogen-containing gas to a heated substrate in a processing vessel toform a carbonitride layer including the element; (b) supplying the gascontaining the element and an oxygen-containing gas to the heatedsubstrate in the processing vessel to form an oxide layer including theelement; and (c) alternately repeating the steps (a) and (b) to form onthe substrate an oxycarbonitride film having the carbonitride layer andthe oxide layer alternately stacked therein.

According to still another aspect of the present invention, there isprovided a substrate processing apparatus including: a processing vesselconfigured to accommodate a substrate; a heater configured to heat thesubstrate in the processing vessel; a element-containing gas supplysystem configured to supply a gas containing an element to the substratein the processing vessel; a carbon-containing gas supply systemconfigured to supply a carbon-containing gas to the substrate in theprocessing vessel; a nitrogen-containing gas supply system configured tosupply a nitrogen-containing gas to the substrate in the processingvessel; an oxygen-containing gas supply system configured to supply anoxygen-containing gas to the substrate in the processing vessel; and acontrol unit configured to control the heater, the element-containinggas supply system, the carbon-containing gas supply system, thenitrogen-containing gas supply system and the oxygen-containing gassupply system to perform (a) supplying the gas containing the element,the carbon-containing gas and the nitrogen-containing gas to the heatedsubstrate in the processing vessel to form a carbonitride layerincluding the element, (b) supplying the gas containing the element andthe oxygen-containing gas to the heated substrate in the processingvessel to form an oxide layer including the element, and (c) alternatelyrepeating (a) and (b) to form on the substrate an oxycarbonitride filmhaving the carbonitride layer and the oxide layer alternately stackedtherein.

According to the present invention, an insulating film having lowpeunittivity, a low etching rate, and a high insulating property can beformed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic configuration view of a vertical processingfurnace of a substrate processing apparatus exemplarily used in anembodiment, showing a longitudinal cross-sectional view of theprocessing furnace;

FIG. 2 is a schematic configuration view of the vertical processingfurnace of the substrate processing apparatus exemplarily used in theembodiment, showing a cross-sectional view taken along line A-A of theprocessing furnace of FIG. 1;

FIG. 3 is a view showing a film-forming flow in a first sequence of theembodiment;

FIG. 4 is a view showing gas supply timing in the first sequence of theembodiment;

FIG. 5 is a view showing a film-forming flow in a second sequence of theembodiment;

FIG. 6 is a view showing gas supply timing in the second sequence of theembodiment;

FIG. 7 is a view showing a film-forming flow in an applied example inthe first sequence of the embodiment;

FIG. 8 is a view showing gas supply timing in the applied example in thefirst sequence of the embodiment;

FIG. 9 is a view showing a film-forming flow in an applied example inthe second sequence of the embodiment;

FIG. 10 is a view showing gas supply timing in the applied example inthe second sequence of the embodiment; and

FIG. 11 is a schematic view of a controller of the substrate processingapparatus exemplarily used in the embodiment.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, an embodiment of the present invention will be describedwith reference to the accompanying drawings.

(1) Configuration of Substrate Processing Apparatus

FIG. 1 is a schematic configuration view of a vertical processingfurnace of a substrate processing apparatus exemplarily used in anembodiment, showing a longitudinal cross-sectional view of theprocessing furnace 202, and FIG. 2 is a schematic configuration view ofthe vertical processing furnace of the substrate processing apparatusexemplarily used in the embodiment, showing a cross-sectional view takenalong line A-A of the processing furnace 202 of FIG. 1.

As shown in FIG. 1, the processing furnace 202 includes a heater 207,which is a heating unit (a heating mechanism). The heater 207 having acylindrical shape is supported and vertically installed by a heater base(not shown), which is a holding plate. In addition, the heater 207functions as an activation mechanism configured to activate a gas usingheat, as will be described later.

A reaction tube 203 constituting a reaction vessel (a processing vessel)is disposed inside the heater 207 to be concentric with the heater 207.The reaction tube 203 is formed of a heat-resistant material such asquartz (SiO₂) or silicon carbide (SiC), and has a cylindrical shape withan upper end closed and a lower end opened. A processing chamber 201 isformed in a hollow tubular portion of the reaction tube 203, and theprocessing chamber 201 is configured to accommodate wafers 200, whichare substrates, using a boat 217, in a state in which the wafers 200 aredisposed in a horizontal posture and arranged in a vertical direction ina multi-stage.

A first nozzle 249 a, a second nozzle 249 b, a third nozzle 249 c and afourth nozzle 249 d are installed in the processing chamber 201 to passthrough a lower portion of the reaction tube 203. A first gas supplypipe 232 a, a second gas supply pipe 232 b, a third gas supply pipe 232c and a fourth gas supply pipe 232 d are connected to the first nozzle249 a, the second nozzle 249 b, the third nozzle 249 c and the fourthnozzle 249 d, respectively. As described above, the four nozzles 249 a,249 b, 249 c and 249 d and the four gas supply pipes 232 a, 232 b, 232 cand 232 d are installed in the reaction tube 203 to supply a pluralityof kinds of gases, here, four kinds of gases, into the processingchamber 201.

In addition, a manifold (not shown) formed of a metal material andconfigured to support the reaction tube 203 may be installed under thereaction tube 203, and each of the nozzles may be installed to passthrough a sidewall of the manifold. In this case, an exhaust pipe 231(to be described later) may be further installed at the manifold formedof a metal material. In addition, even in this case, the exhaust pipe231 may be installed at a lower portion of the reaction tube 203, ratherthan the manifold formed of the metal material. As described above, afurnace port part of the processing furnace 202 may be formed of a metalmaterial, and the nozzles may be installed at the furnace port partformed of the metal material.

A mass flow controller (MFC) 241 a, which is a flow rate control device(a flow rate control unit), and a valve 243 a, which is anopening/closing valve, are installed at the first gas supply pipe 232 ain sequence from an upstream side. In addition, a first inert gas supplypipe 232 e is connected to the first gas supply pipe 232 a at adownstream side of the valve 243 a. An MFC 241 e, which is a flow ratecontrol device (a flow rate control unit), and a valve 243 e, which isan opening/closing valve, are installed at the first inert gas supplypipe 232 e in sequence from an upstream side. Further, the first nozzle249 a is connected to a front end of the first gas supply pipe 232 a.The first nozzle 249 a is vertically installed in an arc-shaped spacebetween an inner wall of the reaction tube 203 and the wafer 200 from alower portion to an upper portion of the inner wall of the reaction tube203 upward in a stacking direction of the wafers 200. That is, the firstnozzle 249 a is disposed at a side of a wafer arrangement region, inwhich the wafers 200 are arranged, and installed at a regionhorizontally surrounding the wafer arrangement region along the waferarrangement region. The first nozzle 249 a is formed of an L-shaped longnozzle, and has a horizontal portion installed to pass through a lowersidewall of the reaction tube 203 and a vertical portion verticallyinstalled from one end side to the other end side of at least the waferarrangement region. A gas supply hole 250 a configured to supply a gasis installed at a side surface of the first nozzle 249 a. The gas supplyhole 250 a is opened toward a center of the reaction tube 203. Aplurality of gas supply holes 250 a are installed from a lower portionto an upper portion of the reaction tube 203, each of the gas supplyholes 250 a having the same opening area and installed at the sameopening pitch. A first gas supply system is mainly constituted by thefirst gas supply pipe 232 a, the MFC 241 a, the valve 243 a and thefirst nozzle 249 a. In addition, a first inert gas supply system ismainly constituted by the first inert gas supply pipe 232 e, the MFC 241e and the valve 243 e.

An MFC 241 b, which is a flow rate control device (a flow rate controlunit) and a valve 243 b, which is an opening/closing valve, areinstalled at the second gas supply pipe 232 b in sequence from anupstream side. In addition, a second inert gas supply pipe 232 f isconnected to the second gas supply pipe 232 b at a downstream side ofthe valve 243 b. An MFC 241 f, which is a flow rate control device (aflow rate control unit), and a valve 243 f, which is an opening/closingvalve, are installed at the second inert gas supply pipe 232 f insequence from an upstream side. In addition, the second nozzle 249 b isconnected to a front end of the second gas supply pipe 232 b. The secondnozzle 249 b is vertically installed in the arc-shaped space between theinner wall of the reaction tube 203 and the wafer 200 from the lowerportion to the upper portion of the inner wall of the reaction tube 203upward in the stacking direction of the wafers 200. That is, the secondnozzle 249 b is disposed at a side of the wafer arrangement region, inwhich the wafers 200 are arranged, and installed at the regionhorizontally surrounding the wafer arrangement region along the waferarrangement region. The second nozzle 249 b is formed of an L-shapedlong nozzle, and has a horizontal portion installed to pass through thelower sidewall of the reaction tube 203 and a vertical portionvertically installed from one end side to the other end side of at leastthe wafer arrangement region. A gas supply hole 250 b configured tosupply a gas is installed at a side surface of the second nozzle 249 b.The gas supply hole 250 b is opened toward the center of the reactiontube 203. A plurality of gas supply holes 250 b are installed from thelower portion to the upper portion of the reaction tube 203, each of thegas supply holes 250 b having the same opening area and installed at thesame opening pitch. A second gas supply system is mainly constituted bythe second gas supply pipe 232 b, the MFC 241 b, the valve 243 b and thesecond nozzle 249 b. In addition, a second inert gas supply system ismainly constituted by the second inert gas supply pipe 232 f, the MFC241 f and the valve 243 f.

An MFC 241 c, which is a flow rate control device (a flow rate controlunit), and a valve 243 c, which is an opening/closing valve, areinstalled at the third gas supply pipe 232 c in sequence from anupstream side. In addition, a third inert gas supply pipe 232 g isconnected to the third gas supply pipe 232 c at a downstream side of thevalve 243 c. An MFC 241 g, which is a flow rate control device (a flowrate control unit), and a valve 243 g, which is an opening/closingvalve, are installed at the third inert gas supply pipe 232 g insequence from an upstream side. Further, the third nozzle 249 c isconnected to a front end of the third gas supply pipe 232 c. The thirdnozzle 249 c is vertically installed in the arc-shaped space between theinner wall of the reaction tube 203 and the wafer 200 from the lowerportion to the upper portion of the inner wall of the reaction tube 203upward in the stacking direction of the wafers 200. That is, the thirdnozzle 249 c is disposed at a side of the wafer arrangement region, inwhich the wafers 200 are arranged, and installed at the regionhorizontally surrounding the wafer arrangement region along the waferarrangement region. The third nozzle 249 c is formed of an L-shaped longnozzle, and has a horizontal portion installed to pass through the lowersidewall of the reaction tube 203 and a vertical portion verticallyinstalled from one end side to the other end side of at least the waferarrangement region. A gas supply hole 250 c configured to supply a gasis installed at a side surface of the third nozzle 249 c. The gas supplyhole 250 c is opened toward the center of the reaction tube 203. Aplurality of gas supply holes 250 c are installed from the lower portionto the upper portion of the reaction tube 203, each of the gas supplyholes 250 b having the same opening area and installed at the sameopening pitch. A third gas supply system is mainly constituted by thethird gas supply pipe 232 c, the MFC 241 c, the valve 243 c and thethird nozzle 249 c. In addition, a third inert gas supply system ismainly constituted by the third inert gas supply pipe 232 g, the MFC 241g and the valve 243 g.

An MFC 241 d, which is a flow rate control device (a flow rate controlunit), and a valve 243 d, which is an opening/closing valve, areinstalled at the fourth gas supply pipe 232 d in sequence from anupstream side. In addition, a fourth inert gas supply pipe 232 h isconnected to the fourth gas supply pipe 232 d at a downstream side ofthe valve 243 d. An MFC 241 h, which is a flow rate control device (aflow rate control unit), and a valve 243 h, which is an opening/closingvalve, are installed at the fourth inert gas supply pipe 232 h insequence from an upstream side. In addition, the fourth nozzle 249 d isconnected to a front end of the fourth gas supply pipe 232 d. The fourthnozzle 249 d is disposed in a buffer chamber 237, which is a gasdistribution space.

The buffer chamber 237 is installed in an arc-shaped space between theinner wall of the reaction tube 203 and the wafer 200 from the lowerportion to the upper portion of the inner wall of the reaction tube 203in the stacking direction of the wafers 20 d. That is, the bufferchamber 237 is disposed at a side of the wafer arrangement region, inwhich the wafers 200 are arranged, and installed at the regionhorizontally surrounding the wafer arrangement region along the waferarrangement region. A gas supply hole 250 e configured to supply a gasis installed at an end of a wall of the buffer chamber 237 adjacent tothe wafer 200. The gas supply hole 250 e is opened toward the center ofthe reaction tube 203. A plurality of gas supply holes 250 e areinstalled from the lower portion to the upper portion of the reactiontube 203, each of the gas supply holes 250 e having the same openingarea and installed at the same opening pitch.

The fourth nozzle 249 d is vertically installed at an end opposite to anend of the buffer chamber 237, at which the gas supply hole 250 e isinstalled, from the lower portion to the upper portion of the inner wallof the reaction tube 203 upward in the stacking direction of the wafers200. That is, the fourth nozzle 249 d is disposed at a side of the waferarrangement region in which the wafers 200 are arranged, and installedat the region surrounding the wafer arrangement region along the waferarrangement region. The fourth nozzle 249 d is formed of an L-shapedlong nozzle, and has a horizontal portion installed to pass through thelower sidewall of the reaction tube 203 and a vertical portionvertically installed from one end side to the other end side of at leastthe wafer arrangement region. A gas supply hole 250 d configured tosupply a gas is installed at a side surface of the fourth nozzle 249 d.The gas supply hole 250 d is opened toward the center of the bufferchamber 237. Similar to the gas supply holes 250 e of the bufferchamber, a plurality of gas supply holes 250 d are installed at thelower portion to the upper portion of the reaction tube 203. While theplurality of gas supply holes 250 d may have the same opening area andthe same opening pitch from the upstream side (the lower portion) to thedownstream side (the upper portion) when a pressure difference betweenthe insides of the buffer chamber 237 and the processing chamber 201 issmall, the gas supply holes 250 d may have opening areas increased fromthe upstream side to the downstream side or opening pitches reduced fromthe upstream side to the downstream side when the pressure difference islarge.

In this embodiment, as the opening areas and the opening pitches of thegas supply holes 250 d of the fourth nozzle 249 d are adjusted from theupstream side to the downstream side as described above, first, while agas passing through each of the gas supply holes 250 d has a differencein a flow velocity, the gas having substantially the same flow rate isinjected. In addition, the gas injected through each of the gas supplyholes 250 d is firstly introduced into the buffer chamber 237, and then,a difference in flow velocity of the gas in the buffer chamber 237 isuniformized.

That is, the gas injected into the buffer chamber 237 through each ofthe gas supply holes 250 d of the fourth nozzle 249 d has a particlespeed attenuated in the buffer chamber 237, and then, is ejected intothe processing chamber 201 through the gas supply holes 250 e of thebuffer chamber 237. Accordingly, the gas injected into the bufferchamber 237 through each of the gas supply holes 250 d of the fourthnozzle 249 d has a unifolin flow rate and flow velocity when the gas isejected into the processing chamber 201 through the gas supply holes 250e of the buffer chamber 237.

A fourth gas supply system is mainly constituted by the fourth gassupply pipe 232 d, the MFC 241 d, the valve 243 d, the fourth nozzle 249d and the buffer chamber 237. In addition, in the fourth gas supplysystem, the buffer chamber 237 functions as a nozzle configured tosupply a gas toward the wafer 200. Further, a fourth inert gas supplysystem is mainly constituted by the fourth inert gas supply pipe 232 h,the MFC 241 h and the valve 243 h.

As described above, a gas supply method in the embodiment includesconveying a gas via the nozzles 249 a, 249 b, 249 c and 249 d and thebuffer chamber 237 disposed in an arc-shaped longitudinally elongatedspace defined by the inner wall of the reaction tube 203 and ends of aplurality of stacked wafers 200, and firstly ejecting the gas into thereaction tube 203 adjacent to the wafers 200 through the gas supplyholes 250 a, 250 b, 250 c, 250 d and 250 e opened in the nozzles 249 a,249 b, 249 c and 249 d and the buffer chamber 237. Here, a main flow ofthe gas in the reaction tube 203 is in a direction parallel to surfacesof the wafers 200, i.e., a horizontal direction. According to the aboveconfiguration, the gas can be uniformly supplied to each of the wafers200, and a film thickness of a thin film formed on each of the wafers200 can be uniformized. In addition, while a remaining gas after thereaction flows in a direction of an exhaust port, i.e., the exhaust pipe231 (to be described later), the flow direction of the remaining gas isappropriately specified by a position of the exhaust port but notlimited to the vertical direction.

A gas containing silicon (Si) (a silicon-containing gas) such as asilicon source gas is supplied into the processing chamber 201 throughthe first gas supply pipe 232 a via the MFC 241 a, the valve 243 a andthe first nozzle 249 a. For example, hexachlorodisilane (Si₂Cl₆,abbreviation: HCD) gas may be used as the silicon-containing gas. Inaddition, when a liquid source material, which is in a liquid state at aroom temperature under an atmospheric pressure, such as HCD is used, theliquid source material is evaporated by an evaporation system such as anevaporator or a bubbler to be supplied as a source gas.

A gas containing carbon (C) (a carbon-containing gas) is supplied intothe processing chamber 201 through the second gas supply pipe 232 b viathe MFC 241 b, the valve 243 b and the second nozzle 249 b. For example,propylene (C₃H₆) gas may be used as the carbon-containing gas. Inaddition, for example, a gas containing hydrogen (H) (ahydrogen-containing gas) may be supplied into the processing chamber 201through the second gas supply pipe 232 b via the MFC 241 b, the valve243 b and the second nozzle 249 b. For example, hydrogen (H₂) gas may beused as the hydrogen-containing gas.

For example, a gas containing nitrogen (N) (a nitrogen-containing gas)is supplied into the processing chamber 201 through the third gas supplypipe 232 c via the MFC 241 c, the valve 243 c and the third nozzle 249c. For example, ammonia (NH₃) gas may be used as the nitrogen-containinggas.

For example, a gas containing oxygen (O) (an oxygen-containing gas) issupplied into the processing chamber 201 through the fourth gas supplypipe 232 d via the MFC 241 d, the valve 243 d, the fourth nozzle 249 dand the buffer chamber 237. For example, oxygen (O₂) gas may be used asthe oxygen-containing gas. In addition, for example, boron (B), that is,a gas containing boron (B) (a boron-containing gas) may be supplied intothe processing chamber 201 through the fourth gas supply pipe 232 d viathe MFC 241 d, the valve 243 d and the fourth nozzle 249 d. For example,boron trichloride (BCl₃) gas or diborane (B₂H₆) gas may be used as theboron-containing gas.

For example, nitrogen (N₂) gas is supplied into the processing chamber201 through the inert gas supply pipes 232 e, 232 f, 232 g and 232 h viathe MFCs 241 e, 241 f, 241 g and 241 h, the valves 243 e, 243 f, 243 gand 243 h, the gas supply pipes 232 a, 232 b, 232 c and 232 d, the gasnozzles 249 a, 249 b, 249 c and 249 d, and the buffer chamber 237.

In addition, for example, when the above-described gases are flowedthrough the gas supply pipes, respectively, a source gas supply system,i.e., a silicon-containing gas supply system (a silane-based gas supplysystem), is constituted by the first gas supply system. In addition, acarbon-containing gas supply system or a hydrogen-containing gas supplysystem is constituted by the second gas supply system. Further, anitrogen-containing gas supply system is constituted by the third gassupply system. Furthermore, an oxygen-containing gas supply system or aboron-containing gas supply system is constituted by the fourth gassupply system. In addition, the source gas supply system may be simplyreferred to as a source supply system. Further, when thecarbon-containing gas, hydrogen-containing gas, nitrogen-containing gas,oxygen-containing gas and boron-containing gas are generally referred toas reaction gases, a reaction gas supply system is constituted by thecarbon-containing gas supply system, the hydrogen-containing gas supplysystem, the nitrogen-containing gas supply system, the oxygen-containinggas supply system and the boron-containing gas supply system.

As shown in FIG. 2, a first rod-shaped electrode 269, which is a firstelectrode, and a second rod-shaped electrode 270, which is a secondelectrode, which have thin and long structures, are disposed in thebuffer chamber 237 from the lower portion to the upper portion of thereaction tube 203 in the stacking direction of the wafers 200. Each ofthe first rod-shaped electrode 269 and the second rod-shaped electrode270 is installed parallel to the fourth nozzle 249 d. Each of the firstrod-shaped electrode 269 and the second rod-shaped electrode 270 iscovered and protected by an electrode protection tube 275, which is aprotection pipe configured to protect each electrode from an upperportion to a lower portion thereof. One of the first rod-shapedelectrode 269 and the second rod-shaped electrode 270 is connected to ahigh frequency power supply 273 via a matching box 272, and the other isconnected to ground, which is a reference potential. As a result, plasmais generated in a plasma generating region 224 between the firstrod-shaped electrode 269 and the second rod-shaped electrode 270. Aplasma source, which is a plasma generator (a plasma generating unit) ismainly constituted by the first rod-shaped electrode 269, the secondrod-shaped electrode 270, the electrode protection tube 275, thematching box 272, and the high frequency power supply 273. In addition,the plasma source functions as an activation mechanism configured toactivate a gas using plasma, which will be described later.

The electrode protection tube 275 has a structure that can be insertedinto the buffer chamber 237 in a state in which each of the firstrod-shaped electrode 269 and the second rod-shaped electrode 270 isisolated from an atmosphere in the buffer chamber 237. Here, when theinside of the electrode protection tube 275 is the same atmosphere asthe external air (atmospheric air), each of the first rod-shapedelectrode 269 and the second rod-shaped electrode 270 inserted into theelectrode protection tube 275 is oxidized by heat transferred from theheater 207. Accordingly, an inert gas purge mechanism configured toprevent oxidation of the first rod-shaped electrode 269 or the secondrod-shaped electrode 270 by substantially suppressing an oxygenconcentration to a low level by charging or purging an inert gas such asnitrogen is installed in the electrode protection tube 275.

The exhaust pipe 231 configured to exhaust the atmosphere in theprocessing chamber 201 is installed at the reaction tube 203. A vacuumpump 246, which is a vacuum exhaust apparatus, is connected to theexhaust pipe 231 via a pressure sensor 245, which is a pressure detector(a pressure detecting unit) configured to detect a pressure in theprocessing chamber 201, and an auto pressure controller (APC) valve 244,which is a pressure regulator (a pressure regulating unit). The APCvalve 244 is an opening/closing valve configured to open/close the valveto perform vacuum exhaust/vacuum exhaust stoppage in the processingchamber 201 in a state in which the vacuum pump 246 is operated, andadjust a valve opening degree to regulate a pressure in the processingchamber 201 in a state in which the vacuum pump 246 is operated. Thepressure in the processing chamber 201 may be vacuum-exhausted to apredetermined pressure (a vacuum level) by adjusting the valve openingdegree of the APC valve 244 based on pressure information detected bythe pressure sensor 245 while operating the vacuum pump 246. An exhaustsystem is mainly constituted by the exhaust pipe 231, the APC valve 244,the vacuum pump 246 and the pressure sensor 245.

A seal cap 219, which is a furnace port cover configured to hermeticallyseal a lower end opening of the reaction tube 203, is installed underthe reaction tube 203. The seal cap 219 contacts a lower end of thereaction tube 203 from a lower side in a vertical direction thereof. Theseal cap 219 is formed of a metal material such as stainless steel, andhas a disc shape. An O-ring 220, which is a seal member in contact withthe lower end of the reaction tube 203, is installed at an upper surfaceof the seal cap 219. A rotary mechanism 267 configured to rotate a boatis installed at the seal cap 219 opposite to the processing chamber 201.A rotary shaft 255 of the rotary mechanism 267 is configured to passthrough the seal cap 219 to be connected to a boat 217 and rotate theboat 217 to rotate the wafers 200. The seal cap 219 is configured to beraised or lowered by a boat elevator 115, which is an elevationmechanism vertically installed at the outside of the reaction tube 203in a vertical direction, and thus, the boat 217 can be loaded/unloadedinto/from the inside of the processing chamber 201.

The boat 217, which is a substrate support, is formed of a heatresistant material such as quartz or silicon carbide, and configured toconcentrically align the plurality of wafers 200 in a horizontal postureand support the wafers 200 in a multi-stage. In addition, an insulatingmember 218 formed of a heat resistant material such as quartz or siliconcarbide is installed under the boat 217 so that heat from the heater 207cannot be easily transferred toward the seal cap 219. In addition, theinsulating member 218 may include a plurality of insulating platesformed of a heat resistant material such as quartz or silicon carbide,and an insulating plate holder configured to support the plates in ahorizontal posture in a multi-stage.

A temperature sensor 263, which is a temperature detector, is installedin the reaction tube 203, and configured to adjust a conduction state tothe heater 207 based on temperature information detected by thetemperature sensor 263 such that the temperature in the processingchamber 201 reaches a predetermined temperature distribution. Similar tothe nozzles 249 a, 249 b, 249 c and 249 d, the temperature sensor 263has an L shape, and is installed along the inner wall of the reactiontube 203.

As shown in FIG. 11, a controller 121, which is a control unit (controlmeans), is constituted by a computer including a central processing unit(CPU) 121 a, a random access memory (RAM) 121 b, a memory device 121 c,and an I/O port 121 d. The RAM 121 b, the memory device 121 c, and theI/O port 121 d are configured to exchange data with the CPU 121 a via aninternal bus 121 e. An input/output device 122 constituted by, forexample, a touch panel is connected to the controller 121.

The memory device 121 c is constituted by, for example, a flash memory,a hard disk drive (HDD), and so on. A control program configured tocontrol an operation of the substrate processing apparatus, or a processrecipe in which sequences or conditions of substrate processing (to bedescribed later) are recorded, is readably stored in the memory device121 c. In addition, the process recipe, which functions as a program, iscombined to execute each sequence of the substrate processing process(to be described later) in the controller 121 and obtain a predeterminedresult. Hereinafter, the process recipe, the control program, or thelike, is generally referred to as, simply, a program. In addition, inthe specification, cases in which the word “program” is used may includecases in which the process recipe is solely included, the controlprogram is solely included, or both of them are included. Further, theRAM 121 b is constituted by a memory region (a work area) in which aprogram, data, etc. read by the CPU 121 a is temporarily held.

The I/O port 121 d is connected to the MFCs 241 a, 241 b, 241 c, 241 d,241 e, 241 f, 241 g and 241 h, the valves 243 a, 243 b, 243 c, 243 d,243 e, 243 f, 243 g and 243 h, the pressure sensor 245, the APC valve244, the vacuum pump 246, the heater 207, the temperature sensor 263,the rotary mechanism 267, the boat elevator 115, the high frequencypower supply 273, the matching box 272, and so on.

The CPU 121 a is configured to read and perform the control program fromthe memory device 121 c and read the process recipe from the memorydevice 121 c in response to an input of an operation command from theinput/output device 122. Then, according to contents of the read processrecipe, the CPU 121 a is configured to control flow rate adjustingoperations of various gases by the MFCs 241 a, 241 b, 241 c, 241 d, 241e, 241 f, 241 g and 241 h, opening/closing operations of the valves 243a, 243 b, 243 c, 243 d, 243 e, 243 f, 243 g and 243 h, anopening/closing operation of the APC valve 244 and a pressure regulatingoperation based on the pressure sensor 245 by the APC valve 244, atemperature adjusting operation of the heater 207 based on thetemperature sensor 263, starting/stoppage of the vacuum pump 246, arotational velocity adjusting operation of the rotary mechanism 267, anelevation operation of the boat 217 by the boat elevator 115, powersupply of the high frequency power supply 273, an impedance adjustingoperation by the matching box 272, and so on.

The controller 121 is not limited to being constituted by an exclusivecomputer but may be constituted by a general-purpose computer. Forexample, an external memory device (for example, a magnetic tape, amagnetic disk such as a flexible disk or a hard disk, an optical discsuch as CD or DVD, a magneto-optical disc such as MO, a semiconductormemory such as a USB memory or a memory card) 123, in which the programis stored, is prepared, and the program is installed on thegeneral-purpose computer using the external memory device 123,configuring the controller 121 according to the embodiment. In addition,a unit for supplying a program to a computer is not limited to the casein which the program is supplied via the external memory device 123. Forexample, the program may be supplied using a communication unit such asthe Internet or an exclusive line, rather than via the external memorydevice 123. Further, the memory device 121 c or the external memorydevice 123 is constituted by a recording medium readable by thecomputer. Hereinafter, these may be generally referred to as, simply, arecording medium. Furthermore, in the specification, cases in which thephrase “recording medium” is used may include cases in which the memorydevice 121 c is solely included, cases in which the external memorydevice 123 is solely included, or cases in which both of them areincluded.

(2) Substrate Processing Process

Hereinafter, as one process of manufacturing a semiconductor deviceusing the processing furnace of the substrate processing apparatus, anexample of a film-forming sequence of forming a silicon oxycarbonitridefilm (a SiOCN film), which is an insulating film, on a substrate will bedescribed. In addition, in the following description, operations ofparts constituting the substrate processing apparatus are controlled bythe controller 121.

In the embodiment of the present invention, a process of supplying asilicon-containing gas, a carbon-containing gas and anitrogen-containing gas to the heated wafer 200 in the processing vesselto form a silicon carbonitride layer (a SiCN layer) having apredetermined thickness, and a process of supplying a silicon-containinggas and an oxygen-containing gas to the heated wafer 200 in theprocessing vessel to form a silicon oxide layer (a SiO layer) having apredetermined thickness are alternately repeated to alternately stackthe silicon carbonitride layer and the silicon oxide layer, forming asilicon oxycarbonitride film (a SiOCN film) having a predeterminedthickness. In this embodiment, since the silicon carbonitride layer andthe silicon oxide layer are alternately stacked on the wafer 200, such afilm-forming method is referred to as a laminate method.

In addition, in a conventional chemical vapor deposition (CVD) method oran atomic layer deposition (ALD) method, for example, in the case of theCVD method, a plurality of kinds of gases including a plurality ofelements constituting a film to be formed are simultaneously supplied,and in the case of the ALD method, a plurality of kinds of gasesincluding a plurality of elements constituting a film to be formed arealternately supplied. Then, supply conditions such as a gas supply flowrate, a gas supply time, plasma power, etc. when a gas is supplied arecontrolled to form a SiO₂ film or a Si₃N₄ film. In these techniques,supply conditions are controlled such that a composition ratio of a filmbecomes 0/Si #2, which is a stoichiometric composition, for example,when the SiO₂ film is formed, and a composition ratio of a film becomesN/Si #1.33, which is a stoichiometric composition, for example, when theSi₃N₄ film is formed.

Here, in the embodiment of the present invention, supply conditions arecontrolled such that a composition ratio of a film to be formed becomesa stoichiometric composition or another predetermined composition ratiodifferent from the stoichiometric composition. For example, supplyconditions are controlled such that at least one of the plurality ofelements constituting the film to be formed is in excess of astoichiometric composition in comparison with another element.Hereinafter, a sequence example of forming a film while controlling aratio of a plurality of elements constituting the film to be formed,i.e., a composition ratio of the film, will be described.

(First Sequence) First, a first sequence of the embodiment will bedescribed. FIG. 3 shows a film-forming flow in the first sequence of theembodiment. FIG. 4 shows gas supply timing in the first sequence of theembodiment.

In the first sequence of the embodiment, a process of supplying asilicon-containing gas to the heated wafer 200 in the processing vesselto form a silicon-containing layer, a process of supplying acarbon-containing gas on the heated wafer 200 in the processing vesselto form a carbon-containing layer on the silicon-containing layer toform a layer including silicon and carbon, a process of supplying anitrogen-containing gas on the heated wafer 200 in the processing vesselto nitride the layer including silicon and carbon to form a siliconcarbonitride layer (a SiCN layer), a process of supplying asilicon-containing gas on the heated wafer 200 in the processing vesselto form a silicon-containing layer, and a process of supplying anoxygen-containing gas on the heated wafer 200 in the processing vesselto oxidize the silicon-containing layer to form a silicon oxide layer (aSiO layer) are set as one cycle, and the cycle is performed apredetermined number of times (n times) to form a siliconoxycarbonitride film (a SiOCN film) having a predetermined filmthickness formed by alternately stacking the silicon carbonitride layerand the silicon oxide layer on the wafer 200. In addition, in the firstsequence of the embodiment, in any of the process of forming the siliconcarbonitride layer and the process of forming the silicon oxide layer, asilicon-containing gas is supplied to the wafer 200 under a condition inwhich a CVD reaction occurs in the process of forming thesilicon-containing layer.

Hereinafter, the first sequence of the embodiment will be described indetail. Here, an example of forming a silicon oxycarbonitride film (aSiOCN film), which is an insulating film, on the wafer 200, which is asubstrate, through a film-forming sequence of FIGS. 3 and 4 using HCDgas, which is a silicon-containing gas, C₃H₆ gas, which is acarbon-containing gas, NH₃ gas, which is a nitrogen-containing gas, andO₂ gas, which is an oxygen-containing gas, will be described.

When the plurality of wafers 200 are charged into the boat 217 (wafercharging), as shown in FIG. 1, the boat 217 supporting the plurality ofwafers 200 is raised by the boat elevator 115 to be loaded into theprocessing chamber 201 (boat loading). In this state, the seal cap 219seals the lower end of the reaction tube 203 via the O-ring 220.

The inside of the processing chamber 201 is vacuum exhausted by thevacuum pump 246 to a desired pressure (a vacuum level). Here, thepressure in the processing chamber 201 is measured by the pressuresensor 245, and the APC valve 244 is feedback-controlled based on themeasured pressure information (pressure regulation). In addition, thevacuum pump 246 always maintains an operation state until processing ofat least the wafer 200 is terminated. Further, the inside of theprocessing chamber 201 is heated by the heater 207 to a desiredtemperature. Here, a conduction state to the heater 207 isfeedback-controlled based on the temperature information detected by thetemperature sensor 263 such that the inside of the processing chamber201 reaches a desired temperature distribution (temperature adjustment).Next, rotation of the boat 217 and the wafer 200 is initiated by therotary mechanism 267. Meanwhile, the rotation of the boat 217 and thewafer 200 by the rotary mechanism 267 is continuously performed untilprocessing of the wafer 200 is terminated. Next, the following fivesteps are sequentially performed.

<SiCN Layer Forming Process>

[Step 1]

The valve 243 a of the first gas supply pipe 232 a is opened to flow HCDgas into the first gas supply pipe 232 a. A flow rate of the HCD gasflowed in the first gas supply pipe 232 a is controlled by the MFC 241a. The flow-rate-controlled HCD gas is supplied into the processingchamber 201 through the gas supply hole 250 a of the first nozzle 249 a,and exhausted through the exhaust pipe 231. Here, the valve 243 e issimultaneously opened to flow an inert gas such as N₂ gas into the inertgas supply pipe 232 e. A flow rate of the N₂ gas flowed in the inert gassupply pipe 232 e is controlled by the MFC 241 e. Theflow-rate-controlled N₂ gas is supplied into the processing chamber 201with the HCD gas and exhausted through the exhaust pipe 231.

At this time, the APC valve 244 is appropriately adjusted such that thepressure in the processing chamber 201 is within a range of, forexample, 10 to 1,000 Pa. A supply flow rate of the HCD gas controlled bythe MFC 241 a is within a range of, for example, 10 to 1,000 sccm. Asupply flow rate of N₂ gas controlled by the MFC 241 e is within a rangeof, for example, 200 to 2,000 sccm. A time for which the wafer 200 isexposed to the HCD gas, i.e., a gas supply time (an irradiation time),is within a range of, for example, 1 to 120 seconds. Here, a temperatureof the heater 207 is set to a temperature at which a CVD reaction isgenerated in the processing chamber 201, i.e., a temperature range ofthe wafer 200 of, for example, 300 to 650° C. In addition, when thetemperature of the wafer 200 is less than 300° C., HCD cannot be easilyadsorbed onto the wafer 200. Further, if the temperature of the wafer200 exceeds 650° C., the CVD reaction is likely to be strong, whichdeteriorates uniformity. Accordingly, the temperature of the wafer 200may have a range of 300 to 650° C.

A silicon-containing layer formed of, for example, less than one atomiclayer to several atomic layers is formed on the wafer (200, a lower basefilm) by supply of the HCD gas. The silicon-containing layer may includean adsorption layer of the HCD gas or a silicon layer (a Si layer) ofthe HCD gas, or both of them. However, the silicon-containing layer maybe a layer including silicon (Si) and chlorine (Cl). Here, a siliconlayer is a generic term including a continuous layer configured bysilicon (Si), a discontinuous layer, or a silicon thin film formed byoverlapping the layers. In addition, a continuous layer configured by Simay be referred to as a silicon thin film. Further, Si constituting thesilicon layer includes Si having a bonding to Cl that is not completelybroken. Furthermore, the adsorption layer of the HCD gas includes achemisorption layer in which a gas molecule of the HCD gas iscontinuous, and a discontinuous chemisorption layer. That is, theadsorption layer of the HCD gas includes a chemisorption layer of onemolecule layer constituted by an HCD molecule or less than one moleculelayer. In addition, the HCD (Si₂Cl₆) molecule constituting theadsorption layer of the HCD gas includes a molecule (a Si_(x)Cl_(y)molecule) in which bonding between Si and Cl is partially broken. Thatis, the adsorption layer of the HCD gas includes a chemisorption layerin which a Si₂Cl₆ molecule and/or a Si_(x)Cl_(y) molecule is continuous,or a discontinuous chemisorption layer. In addition, a layer of lessthan one atomic layer means an atomic layer which is discontinuouslyformed, and a layer of one atomic layer means an atomic layer which iscontinuously formed. Further, a layer of less than one molecule layermeans a molecule layer which is discontinuously formed, and a layer ofone molecule layer means a molecule layer which is continuously formed.Under a condition in which the HCD gas is self-decomposed (pyrolysis),i.e., under a condition in which a pyrolysis reaction of HCD occurs, Siis deposited on the wafer 200 to form a silicon layer. Under a conditionin which the HCD gas is not self-decomposed (pyrolysis), i.e., under acondition in which a pyrolysis reaction of HCD does not occur, the HCDgas is adsorbed onto the wafer 200 to form an adsorption layer of theHCD gas. In addition, rather than forming the adsorption layer of theHCD gas on the wafer 200, formation of the silicon layer on the wafer200 may increase a thin-film forming rate. When a thickness of thesilicon-containing layer formed on the wafer 200 exceeds several atomiclayers, action of nitridation in the following Step 3 does not reach theentire silicon-containing layer. Further, a minimum value of thesilicon-containing layer that can be formed on the wafer 200 is lessthan one atomic layer. Accordingly, a thickness of thesilicon-containing layer may be from less than one atomic layer toseveral atomic layers. Furthermore, when a thickness of thesilicon-containing layer is one atomic layer or less, i.e., one atomiclayer or less than one atomic layer, action of a nitridation reaction inthe following Step 3 may be relatively increased to a reduction in timerequired for the nitridation reaction of Step 3. The time required toform the silicon-containing layer in Step 1 may be reduced. Eventually,since a processing time per one cycle can be reduced, a total processingtime can also be reduced. That is, the film-forming rate can also beincreased. In addition, when the thickness of the silicon-containinglayer is one atomic layer or less, controllability of film thicknessuniformity can be increased.

After the silicon-containing layer is formed, supply of the HCD gas isstopped. Here, in a state in which the APC valve 244 of the exhaust pipe231 is open, the inside of the processing chamber 201 is vacuumexhausted by the vacuum pump 246 to eliminate gases remaining in theprocessing chamber 201 such as non-reacted HCD gas. In addition, here,the valve 243 e is kept open, and supply of N₂ gas into the processingchamber 201 is maintained. Accordingly, an elimination of the gasesremaining in the processing chamber 201 is facilitated.

As the silicon-containing gas, in addition to hexachlorodisilane(Si₂Cl₆, abbreviation: HCD) gas, not only an inorganic source such astetrachlorosilane, i.e., silicon tetrachloride (SiCl₄, abbreviation:STC) gas, trichlorosilane (SiHCl₃, abbreviation: TCS) gas,dichlorosilane (SiH₂Cl₂, abbreviation: DCS) gas, monochlorosilane(SiH₃Cl, abbreviation: MCS) gas, and monosilane (SiH₄) gas, but also anorganic source such as aminosilane-based tetrakisdimethylaminosilane(Si[N(CH₃)₂]₄, abbreviation: 4DMAS) gas, trisdimethylaminosilane(Si[N(CH₃)₂]₃H, abbreviation: 3DMAS) gas, bisdiethylaminosilane(Si[N(C₂H₅)₂]₂H₂, abbreviation: 2DEAS) gas, bistertiarybutylaminosilane(SiH₂[NH(C₄H₉)]₂, abbreviation: BTBAS) gas, and hexamethyldisilazane((CH₃)₃SiNHSi(CH₃)₃, abbreviation: HMDS) gas may be used. As an inertgas, in addition to N₂ gas, a rare gas such as Ar gas, He gas, Ne gas,and Xe gas may be used.

[Step 2]

After Step 1 is terminated and the remaining gas in the processingchamber 201 is removed, the valve 243 b of the second gas supply pipe232 b is opened to flow C₃H₆ gas into the second gas supply pipe 232 b.A flow rate of the C₃H₆ gas flowed in the second gas supply pipe 232 bis controlled by the MFC 241 b. The flow-rate-controlled C₃H₆ gas issupplied into the processing chamber through the gas supply hole 250 bof the second nozzle 249 b and exhausted through the exhaust pipe 231.In addition, the C₃H₆ gas supplied into the processing chamber 201 isactivated by heat. Here, the valve 243 f is simultaneously opened toflow N₂ gas into the inert gas supply pipe 232 f. The N₂ gas is suppliedinto the processing chamber 201 with the C₃H₆ gas, and exhausted throughthe exhaust pipe 231.

Here, the APC valve 244 is appropriately adjusted such that the pressurein the processing chamber 201 is within a range of, for example, 50 to3,000 Pa. The supply flow rate of the C₃H₆ gas controlled by the MFC 241b is within a range of, for example, 100 to 10,000 sccm. The supply flowrate of the N₂ gas controlled by the MFC 241 f is within a range of, forexample, 200 to 2,000 sccm. Here, a partial pressure of the C₃H₆ gas inthe processing chamber 201 is within a range of 6 to 2,940 Pa. A timefor which the wafer 200 is exposed to the C₃H₆ gas, i.e., a gas supplytime (an irradiation time), is within a range of, for example, 1 to 120seconds. Similar to Step 1, the temperature of the heater 207 at thistime is set such that the temperature of the wafer 200 is within a rangeof 300 to 650° C. In addition, activating the C₃H₆ gas by heat enablessoft reaction and facilitates the formation of a carbon-containing layer(to be described later).

Here, the gas flowing into the processing chamber 201 is a thermallyactivated C₃H₆ gas, and the HCD gas does not flow in the processingchamber 201. Accordingly, the C₃H₆ gas is supplied to the wafer 200 inan activated state in which no gas phase reaction occurs, and at thistime, a carbon-containing layer of less than one atomic layer, i.e., adiscontinuous carbon-containing layer, is formed on thesilicon-containing layer formed on the wafer 200 in Step 1. Accordingly,a second layer including silicon and carbon is formed. In addition,according to conditions, a portion of the silicon-containing layer maybe reacted with the C₃H₆ gas to modify (carbonize) thesilicon-containing layer to form a second layer including silicon andcarbon.

The carbon-containing layer formed on the silicon-containing layer maybe a carbon layer (a C layer), or a chemisorption layer of thecarbon-containing gas (a C₃H₆ gas), i.e., a chemisorption layer of amaterial (C_(x) H_(y)) decomposed from C₃H₆. Here, the carbon layershould be a discontinuous layer formed by carbon. In addition, thechemisorption layer of C_(x)H_(y) should be a chemisorption layer inwhich a C_(x)H_(y) molecule is discontinuous. Further, when thecarbon-containing layer formed on the silicon-containing layer is acontinuous layer, for example, when an adsorption state of C_(x)H_(y)onto the silicon-containing layer is in a saturation state, and acontinuous chemisorption layer of C_(x)H_(y) on the silicon-containinglayer is formed, a surface of the silicon-containing layer is entirelycovered by the chemisorption layer of C_(x)H_(y). In this case, assilicon is not present on a surface of the second layer, a nitridationreaction of the second layer in Step 3 (to be described later) becomesdifficult. This is because nitrogen is bonded to silicon but is notbonded to carbon. In order to cause the nitridation reaction desired inStep 3 (to be described later), an adsorption state of C_(x)H_(y) ontothe silicon-containing layer is in an unsaturated state, and siliconshould be exposed to the surface of the second layer.

In addition, in order to change the adsorption state of C_(x)H_(y) ontothe silicon-containing layer to the unsaturated state, the processingconditions in Step 2 may be the above-mentioned processing conditions.However, when the processing conditions in Step 2 are replaced with thefollowing processing conditions, the adsorption state of C_(x)H_(y) ontothe silicon-containing layer can be easily changed to the unsaturatedstate.

Wafer temperature: 500 to 630° C.

Pressure in processing chamber: 133 to 2,666 Pa

C₃H₆ gas partial pressure: 67 to 2,515 Pa

C₃H₆ gas supply flow rate: 1,000 to 5,000 sccm

N₂ gas supply flow rate: 300 to 1,000 sccm

C₃H₆ gas supply time: 6 to 100 seconds

After that, the valve 243 b of the second gas supply pipe 232 b isclosed to stop supply of the C₃H₆ gas. Here, in a state in which the APCvalve 244 of the exhaust pipe 231 is open, the inside of the processingchamber 201 is vacuum exhausted by the vacuum pump 246 to eliminategases remaining in the processing chamber 201 such as the non-reactedC₃H₆ gas and reaction byproducts remaining in the processing chamber201. In addition, here, the valve 243 f is kept open, and supply of N₂gas into the processing chamber 201 is maintained. Accordingly,eliminations of the gases remaining in the process chamber 201 and thereaction byproducts remaining in the processing chamber 201 arefacilitated.

As the carbon-containing gas, in addition to propylene (C₃H₆) gas,acetylene (C₂H₂) gas, ethylene (C₂H₄) gas, or the like may be used.

[Step 3]

After removing the remaining gas in the processing chamber 201, thevalve 243 c of the third gas supply pipe 232 c is opened to flow NH₃ gasinto the third gas supply pipe 232 c. A flow rate of the NH₃ gas flowedin the third gas supply pipe 232 c is controlled by the MFC 241 c. Theflow-rate-controlled NH₃ gas is supplied into the processing chamber 201through the gas supply hole 250 c of the third nozzle 249 c andexhausted through the exhaust pipe 231. In addition, the NH₃ gassupplied into the processing chamber 201 is activated by heat. At thistime, the valve 243 g is simultaneously opened to flow N₂ gas into theinert gas supply pipe 232 g. The N₂ gas is supplied into the processingchamber 201 with the NH₃ gas and exhausted through the exhaust pipe 231.

When the NH₃ gas is activated by heat and flowed, the APC valve 244 isappropriately adjusted such that the pressure in the processing chamber201 is within a range of, for example, 50 to 3,000 Pa. A supply flowrate of the NH₃ gas controlled by the MFC 241 c is within a range of,for example, 100 to 10,000 sccm. A supply flow rate of the N₂ gascontrolled by the MFC 241 g is within a range of, for example, 200 to2,000 sccm. Here, a partial pressure of the NH₃ gas in the processingchamber 201 is within a range of 6 to 2,940 Pa. A time for which thewafer 200 is exposed to the NH₃ gas, i.e., a gas supply time (anirradiation time), is within a range of, for example, 1 to 120 seconds.The temperature of the heater 207 at this time is set such that thetemperature of the wafer 200 is within a range of 300 to 650° C.,similar to Step 1. Since NH₃ gas has a high reaction temperature andcannot be easily reacted at the above-mentioned wafer temperature, thepressure in the processing chamber 201 becomes a relatively highpressure as described above to enable thermal activation. In addition,then al activation and supply of the NH₃ gas can cause a soft reaction,and nitridation (to be described later) can be softly perfonned.

The gas flowing into the processing chamber 201 is the then iallyactivated NH₃ gas, and neither HCD gas nor C₃H₆ gas flows in theprocessing chamber 201. Accordingly, the NH₃ gas does not cause a gasphase reaction, and the activated NH₃ gas reacts with a portion of thelayer including silicon and carbon, which is the second layer formed onthe wafer 200 in Step 2. As a result, the second layer is thermallynitrided with non-plasma, and changed (modified) to a third layerincluding silicon, carbon and nitrogen, i.e., a silicon carbonitridelayer (a SiCN layer).

Here, the nitridation reaction of the second layer is set not to besaturated. For example, when a silicon layer of several atomic layers isformed in Step 1 and a carbon-containing layer of less than one atomiclayer is formed in Step 2, a portion of a surface layer thereof (oneatomic layer of the surface) is nitrided. That is, a portion of theregion or the entire region in which nitridation of the surface layercan occur (a silicon-exposed region) is nitrided. In this case, thenitridation is performed under a condition in which the nitridationreaction of the second layer is unsaturated, so that the entire secondlayer is not nitrided. In addition, while several layers of the secondlayer below the surface layer may be nitrided according to conditions,only nitridation of the surface layer can improve controllability of thecomposition ratio of the silicon oxycarbonitride film. In addition, forexample, even when a silicon layer of one atomic layer or less than oneatomic layer is formed in Step 1 and a carbon-containing layer of lessthan one atomic layer is formed in Step 2, a portion of the surfacelayer is similarly nitrided. Even in this case, nitridation is performedunder a condition in which the nitridation reaction of the second layeris unsaturated, so that the entire second layer is not nitrided.

In addition, in order for the nitridation reaction of the second layerto be unsaturated, the processing conditions in Step 3 may be theabove-mentioned processing conditions. However, when the processingconditions in Step 3 are replaced with the following processingconditions, the nitridation reaction of the second layer can be easilyunsaturated.

Wafer temperature: 500 to 630° C.

Pressure in processing chamber: 133 to 2,666 Pa

NH₃ gas partial pressure: 67 to 2,515 Pa

NH₃ gas supply flow rate: 1,000 to 5,000 sccm

N₂ gas supply flow rate: 300 to 1,000 sccm

NH₃ gas supply time: 6 to 100 seconds

Next, the valve 243 c of the third gas supply pipe 232 c is closed tostop supply of the NH₃ gas. At this time, the APC valve 244 of theexhaust pipe 231 is kept open, and the inside of the processing chamber201 is vacuum exhausted by the vacuum pump 246 to eliminate gasesremaining in the processing chamber 201 such as the non-reacted NH₃ gasand reaction byproducts remaining in the processing chamber 201. Inaddition, here, the valve 243 g is kept open, and supply of the N₂ gasinto the processing chamber 201 is maintained. Accordingly, eliminationsof the gases remaining in the process chamber 201 and the reactionbyproducts remaining in the processing chamber 201 are facilitated.

As the nitrogen-containing gas, in addition to ammonia (NH₃) gas,diazine (N₂H₂) gas, hydrazine (N₂H₄) gas, N₃H₈ gas or the like may beused.

<SiO Layer Forming Process>

[Step 4]

After the remaining gas in the processing chamber 201 is removed,similar to Step 1, HCD gas is supplied into the processing chamber 201and exhausted to form a silicon-containing layer, which is a fourthlayer, on the SiCN layer (the third layer) formed on the wafer 200 inStep 3. After the silicon-containing layer is formed, similar to Step 1,supply of the HCD gas is stopped to remove the remaining gas in theprocessing chamber 201. In addition, the opening/closing operations ofthe valves, the processing conditions, the generated reactions, theformed layers, the remaining gas removal method, and the usable gases inStep 4 are similar to that in Step 1.

[Step 5]

After the remaining gas in the processing chamber 201 is removed, thevalve 243 d of the fourth gas supply pipe 232 d and the valve 243 h ofthe fourth inert gas supply pipe 232 h are opened to flow O₂ gas intothe fourth gas supply pipe 232 d and to flow N₂ gas into the fourthinert gas supply pipe 232 h. A flow rate of the N₂ gas flowed in thefourth inert gas supply pipe 232 h is controlled by the MFC 241 h. Aflow rate of the O₂ gas flowed in the fourth gas supply pipe 232 d iscontrolled by the MFC 241 d. The flow-rate-controlled O₂ gas is mixedwith the flow-rate-controlled N₂ gas in the fourth gas supply pipe 232 dto be supplied into the buffer chamber 237 through the gas supply hole250 d of the fourth nozzle 249 d. Here, no high frequency power isapplied between the first rod-shaped electrode 269 and the secondrod-shaped electrode 270. Accordingly, the O₂ gas supplied into thebuffer chamber 237 is activated with heat, supplied into the processingchamber 201 toward the wafer 200 through the gas supply hole 250 e, andexhausted through the exhaust pipe 231. In addition, here, highfrequency power may be applied between the first rod-shaped electrode269 and the second rod-shaped electrode 270 to activate the O₂ gassupplied into the buffer chamber 237 with plasma.

When the O₂ gas is activated with heat and flowed, the APC valve 244 isappropriately adjusted so that the pressure in the processing chamber201 is within a range of, for example, 1 to 3,000 Pa. A supply flow rateof the O₂ gas controlled by the MFC 241 d is within a range of, forexample, 100 to 5,000 sccm (0.1 to 5 slm). A supply flow rate of the N₂gas controlled by the MFC 241 h is within a range of, for example, 200to 2,000 sccm (0.2 to 2 slm). Here, a partial pressure of the O₂ gas inthe processing chamber 201 is within a range of 6 to 2,940 Pa. A timefor which the wafer 200 is exposed to the O₂ gas, i.e., a gas supplytime (an irradiation time), is within a range of, for example, 1 to 120seconds. A temperature of the heater 207 at this time is set such thatthe temperature of the wafer 200 is within a range of 300 to 650° C.,similar to Steps 1 to 3. The O₂ gas is thermally activated under thesame conditions as described above. In addition, as the O₂ gas isactivated with heat and supplied, soft reaction can be generated andoxidation (to be described later) can be softly performed.

Here, the gas flowing into the processing chamber 201 is the thermallyactivated O₂ gas, and neither HCD gas, C₃H₆ gas nor NH₃ gas flows in theprocessing chamber 201. Accordingly, the O₂ gas does not cause a gasphase reaction, and the activated O₂ gas reacts with at least a portionof the silicon-containing layer (the fourth layer) formed on the SiCNlayer (the third layer) formed in Step 4. Accordingly, thesilicon-containing layer is thermally oxidized with non-plasma to bechanged (modified) into a fifth layer including silicon and oxygen,i.e., a silicon oxide layer (a SiO₂ layer, hereinafter simply referredto as a SiO layer). Accordingly, a silicon oxycarbonitride layer (aSiOCN layer), in which the SiO layer is stacked on the SiCN layer, isformed. Here, the activated O₂ gas may be reacted with at least aportion of the silicon-containing layer, or may be reacted with at leasta portion of the SiCN layer, which is an under layer thereof. That is,at least a portion of the SiCN layer, which is an under layer of thesilicon-containing layer, may be thermally oxidized with non-plasma.

Here, an oxidation reaction of the silicon-containing layer is set to beunsaturated. For example, when the silicon layer of several atomiclayers is formed in Step 4, at least a portion of the surface layer (oneatomic layer of the surface) is oxidized. In this case, in order not tooxidize the entire silicon layer, oxidation is performed under acondition in which the oxidation reaction of the silicon layer isunsaturated. In addition, while several layers from the surface layer ofthe silicon layer may be oxidized according to conditions, only thesurface layer may be oxidized to improve controllability of thecomposition ratio of the SiOCN film. In addition, for example, even whenthe silicon layer of one atomic layer or less than one atomic layer isformed in Step 4, similarly, a portion of the surface layer is oxidized.Even in this case, in order not to oxidize the entire silicon layer,oxidation is performed under a condition in which the oxidation reactionof the silicon layer is unsaturated. Here, even when at least a portionof the SiCN layer, which is an under layer of the silicon-containinglayer, is oxidized, the oxidation reaction of the SiCN layer is set tobe unsaturated. In this case, in order not to oxidize the entire SiCNlayer, the oxidation is performed under a condition in which theoxidation reaction of the SiCN layer is unsaturated.

In addition, in order for the oxidation reaction of thesilicon-containing layer (the fourth layer) or the SiCN layer (the thirdlayer), which is an under layer thereof, to be unsaturated, theprocessing conditions in Step 5 may be the above-mentioned processingconditions. However, when the processing conditions in Step 5 arereplaced with the following processing conditions, the oxidationreaction of the silicon-containing layer or the SiCN layer can be easilyunsaturated.

Wafer temperature: 500 to 630° C.

Pressure in processing chamber: 133 to 2,666 Pa

O₂ gas partial pressure: 67 to 2,515 Pa

O₂ gas supply flow rate: 1,000 to 5,000 sccm

N₂ gas supply flow rate: 300 to 1,000 sccm

O₂ gas supply time: 6 to 100 seconds

Next, the valve 243 d of the fourth gas supply pipe 232 d is closed tostop supply of the O₂ gas. At this time, the APC valve 244 of theexhaust pipe 231 is kept open, and the inside of the processing chamber201 is vacuum exhausted by the vacuum pump 246 to eliminate gasesremaining in the processing chamber 201 such as non-reacted O₂ gas.Here, the valve 243 h is kept open, and supply of the N₂ gas into theprocessing chamber 201 is maintained. Accordingly, an elimination of thegases remaining in the processing chamber 201 is facilitated.

As the oxygen-containing gas, in addition to the oxygen (O₂) gas, vapor(H₂O) gas, nitrogen oxide (NO) gas, nitrous oxide (N₂O) gas, nitrogendioxide (NO₂) gas, carbon oxide (CO) gas, carbon dioxide (CO₂) gas,ozone (O₃) gas, O₃ gas+H₂ gas, O₃ gas+H₂ gas, and so on may be used.

Steps 1 to 5 (described above) are set as one cycle, and the cycle isperformed a predetermined number of times (one time or more), so thatthe SiCN layer and the SiO layer can be alternately stacked on the wafer200 to form a thin film having a predetermined film thickness andincluding silicon, carbon, nitrogen and oxygen, i.e., a siliconoxycarbonitride film (a SiOCN film). In addition, the above-mentionedcycle may be repeated a plurality of times.

In each step, as the pressure in the processing chamber 201 or theprocessing conditions of the gas supply time, and so on are controlled,a ratio of the respective elements, i.e., a silicon element, an oxygenelement, a carbon element, and a nitrogen element in the SiOCN layer,i.e., a silicon concentration, an oxygen concentration, a carbonconcentration, and a nitrogen concentration, can be adjusted to controlthe composition ratio of the SiOCN film.

In addition, here, as a thickness of at least one layer of the SiCNlayer and the SiO layer is controlled, a composition ratio of the SiOCNfilm may be controlled. For example, when the SiCN layer having athickness of several atomic layers and the SiO layer having a thicknessof less than one atomic layer are alternately stacked, a ratio of thesilicon element, the nitrogen element and the carbon element withrespect to the oxygen element in the SiOCN film is controlled to beenriched (a ratio of the oxygen element becomes poor). In addition, forexample, when the SiCN layer having a thickness of less than one atomiclayer and the SiO layer having a thickness of several atomic layers arealternately stacked, a ratio of the silicon element and the oxygenelement with respect to the nitrogen element and the carbon element inthe SiOCN film is controlled to be enriched (a ratio of the nitrogenelement and the carbon element becomes poor). In addition, according tothe processing conditions, the SiCN layer and the SiO layer, which arealternately stacked, may be diffused to each other.

When a film-forming processing of forming the SiOCN film having apredetermined film thickness and including a predetermined compositionis performed, an inert gas such as N₂ is supplied into the processingchamber 201 and exhausted so that the inside of the processing chamber201 is purged by the inert gas (purging). Next, the atmosphere in theprocessing chamber 201 is substituted with the inert gas (inert gassubstitution), and the inside of the processing chamber 201 is returnedto an atmospheric pressure (return to atmospheric pressure).

Next, in a state in which the seal cap 219 is lowered by the boatelevator 115 to open the lower end of the reaction tube 203 and theprocessed wafer 200 is supported by the boat 217, the boat 217 isunloaded to the outside of the reaction tube 203 from the lower end ofthe reaction tube 203 (boat unloading). Next, the processed wafer 200 isdischarged from the boat 217 (wafer discharging).

(Second Sequence)

Hereinafter, a second sequence of the embodiment will be described. FIG.5 is a view showing a film-forming flow in the second sequence of theembodiment. FIG. 6 is a view showing gas supply timing in the secondsequence of the embodiment.

In the first sequence, the example in which Steps 1 to 5 (describedabove) are set as one cycle and the cycle is performed one time or more,and the SiCN layer of one layer and the SiO layer of one layer arealternately stacked on the wafer 200 to form the SiOCN film having apredetermined film thickness has been described.

Meanwhile, in the second sequence, a process of performing a first setincluding Steps 1 to 3 (described above) a predetermined number of times(one time or more) to form a SiCN layer having a predeterminedthickness, and a process of performing a second set including Steps 4and 5 a predetermined number of times (one time or more) to form a SiOlayer having a predetermined thickness are set as one cycle, and thecycle is performed a predetermined number of times (one time or more),to form a SiOCN film having a predetermined thickness and formed byalternately stacking a SiCN layer of one layer or more and a SiO layerof one layer or more on the wafer 200. That is, in the second sequence,the SiCN layer of one layer or more, for example, several layers, andthe SiO layer of one layer or more, for example, several layers, arealternately stacked on the wafer 200 to form the SiOCN film having apredetermined thickness.

More specifically, in the second sequence of the embodiment, a processin which a process of supplying a silicon-containing gas to the heatedwafer 200 in the processing vessel to form a silicon-containing layer, aprocess of supplying a carbon-containing gas to the heated wafer 200 inthe processing vessel to form a carbon-containing layer on thesilicon-containing layer to form a layer including silicon and carbon,and a process of supplying a nitrogen-containing gas to the heated wafer200 in the processing vessel to nitride the layer including silicon andcarbon to form a silicon carbonitride layer are set as a first set ofprocesses, and the first set is performed a predetermined number oftimes (x times) to form a silicon carbonitride layer (a SiCN layer)having a predetermined thickness; and a process in which a process ofsupplying a silicon-containing gas to the heated wafer 200 in theprocessing vessel to form a silicon-containing layer, and a process ofsupplying an oxygen-containing gas to the heated wafer 200 in theprocessing vessel to oxidize the silicon-containing layer to form asilicon oxide layer are set as a second set of processes, and the secondset is performed a predetermined number of times (y times) to form asilicon oxide layer (a SiO layer) having a predetermined thickness; areset as one cycle, and the cycle is performed a predetermined number oftimes (n times) to form a silicon oxycarbonitride film (SiOCN film)having a predetermined thickness and formed by alternately stacking thesilicon carbonitride layer and the silicon oxide layer on the wafer 200.

Even in this case, the above-mentioned cycle may be repeated a pluralityof times. In addition, even in the second sequence of the embodiment, inany process of the process of forming the silicon carbonitride layer andthe process of forming the silicon oxide layer, a silicon-containing gasis supplied to the wafer 200 under a condition in which a CVD reactionoccurs, in the process of forming the silicon-containing layer.

In addition, the second sequence is distinguished from the firstsequence in that the number of times (x) that the SiCN layer formingprocess is performed is different from the number of times (y) that theSiO layer forming process is performed, but the other operations aresimilar to the first sequence. That is, the opening/closing operationsof the respective valves, processing conditions, generated reactions,formed layers, a remaining gas removal method, usable gases, and so onin the SiCN layer forming process and the SiO layer forming process inthe second sequence are similar to those of the first sequence. Further,the wafer charging, boat loading, pressure regulation, temperatureadjustment, wafer rotation, purging, inert gas substitution, return toatmospheric pressure, boat unloading, and wafer discharging in thesecond sequence are similarly performed in the first sequence.Furthermore, the case in which the number of times (x) that the SiCNlayer forming process is performed and the number of times (y) that theSiO layer forming process is performed in the second sequence are eachone time (x=1 and y=1) corresponds to the first sequence.

FIG. 6 shows an example in which Steps 1 to 3 (described above) are setas a first set, the first set is performed two times, Step 4 and 5 areset as a second set, the second set is performed one time, these are setas one cycle, and the cycle is performed n times, so that a SiCN layerof two layers and a SiO layer of one layer are alternately stacked onthe wafer 200 to form a SiOCN film having a predetermined filmthickness.

As described above, Steps 1 to 3 (to be described later) are set as afirst set, the first set is performed a predetermined number of times (xtimes), Steps 4 and 5 are set as a second set, the second set isperformed a predetermined number of times (y times), these are set asone cycle, and the cycle is performed a predetermined number of times (ntimes), so that a ratio of a silicon element, a carbon element and anitrogen element with respect to an oxygen element or a ratio of asilicon element and an oxygen element with respect to a carbon elementand a nitrogen element in a SiOCN film can be appropriately controlled,and controllability of a composition ratio of the SiOCN film can befurther improved. For example, when a SiCN layer of five layers and aSiO layer of one layer are alternately stacked, a ratio of a siliconelement, a nitrogen element and a carbon element with respect to anoxygen element in the SiOCN film can be controlled to be enriched (aratio of the oxygen element becomes poor). In addition, for example,when a SiCN layer of one layer and a SiO layer of five layers arealternately stacked, a ration of a silicon element and an oxygen elementwith respect to a nitrogen element and a carbon element in a SiOCN filmcan be controlled to be enriched (a ratio of the nitrogen element andthe carbon element becomes poor). That is, as a layer number of at leastone of the SiCN layer and the SiO layer, i.e., a set number (x, y) iscontrolled, the composition ratio of the SiOCN film can be preciselycontrolled, and according to a combination of the set number (x, y),minute composition control in which a ratio of a certain element is asmall amount (for example, several %) becomes possible. In addition, aseach set number is increased, a layer number of the SiCN layer or theSiO layer formed in one cycle can be increased by the number of sets, acycle rate can be improved, and a film-forming rate can also beimproved.

(3) Effects According to the Embodiment

According to the embodiment, one or a plurality of effects describedbelow are provided.

According to the embodiment, in the first sequence, since Steps 1 to 5are set as one cycle and the cycle is performed a predetermined numberof times to form the SiOCN film having a predetermined film thickness,the SiOCN film having a predetermined composition and a predeterminedfilm thickness can be formed. In addition, in the second sequence, sinceSteps 1 to 3 are set as a first set, the first set is performed apredetermined number of times, Steps 4 and 5 are set as a second set,the second set is performed a predetermined number of times, these areset as one cycle, and the cycle is performed a predetermined number oftimes to form the SiOCN film having a predetermined film thickness, theSiOCN film having a predetermined composition and a predetermined filmthickness can be formed.

In addition, according to the embodiment, rather than directly oxidizingthe SiCN layer, since the SiCN layer and the SiO layer are alternatelystacked to form the SiOCN layer through a laminate method, separation ofC or N from the SiCN layer when the SiCN layer is directly oxidized canbe prevented. That is, since a bonding force of Si—O bonding is strongerthan that of Si—C bonding or Si—N bonding in the SiCN layer, when theSiCN layer is directly oxidized, during a process of forming the Si—Obonding, the Si—C bonding and the Si—N bonding in the SiCN layer may bebroken, and C and N in which bonding to Si is broken may be separated.However, since deposition of the SiCN layer onto the wafer anddeposition of the SiO layer onto the SiCN layer are alternatelyperformed, and the SiCN layer and the SiO layer are alternately stackedto form the SiOCN layer, the SiOCN layer can be formed without directlyoxidizing the SiCN layer, and separation of C and N from the SiCN layercan be prevented. Accordingly, a decrease in a C concentration or an Nconcentration in the SiOCN film can be prevented, controllability of thecomposition ratio control of the SiOCN film can be improved, and acomposition ratio control window can be widened.

Further, in the embodiment, in Step 5, while oxidation processing withrespect to a stacking film of the silicon-containing layer and the SiCNlayer is performed, the silicon-containing layer formed on the SiCNlayer in Step 4 is actively oxidized, and the silicon-containing layerfunctions as an oxidation blocking layer configured to block oxidationof the SiCN layer. Here, while at least a portion of the SiCN layer,which is an under layer of the silicon-containing layer, may beoxidized, even in this case, oxidation of the SiCN layer is suppressedby an oxidation blocking effect of the silicon-containing layer, anoxidation reaction of the SiCN layer can be easily unsaturated, andseparation of C or N from the SiCN layer can be suppressed.

In addition, when the SiCN layer is directly oxidized, in order tosuppress separation of C or N from the SiCN layer, oxidation of the SiCNlayer by the oxygen-containing gas should be stopped while unsaturated.However, in this embodiment, since the silicon-containing layer formedon the SiCN layer in Step 4 functions as an oxidation blocking layerconfigured to prevent oxidation of the SiCN layer, in oxidation of thesilicon-containing layer by the oxygen-containing gas in Step 5, thereis no need to use an unsaturated region, and use of a saturated regionbecomes possible. That is, saturation of the oxidation reaction of thesilicon-containing layer becomes possible while suppressing separationof C or N from the SiCN layer. Here, while at least a portion of theSiCN layer, which is an under layer of the silicon-containing layer, maybe oxidized, even in this case, oxidation of the SiCN layer issuppressed by an oxidation blocking effect of the silicon-containinglayer so that the oxidation reaction of the SiCN layer is easilyunsaturated and separation of C or N from the SiCN layer can besuppressed. That is, according to the embodiment, while suppressingseparation of C or N from the SiCN layer, an oxidation force of thesilicon-containing layer can be increased by the oxygen-containing gasin Step 5, and more uniform oxidation processing becomes possible. As aresult, improvement in a film-forming rate of the SiOCN film andimprovement in film thickness uniformity in the wafer surface becomepossible.

Further, according to the embodiment, in either of the first sequenceand the second sequence, the SiOCN film having good film thicknessuniformity in the wafer surface can be formed. In addition, when theSiOCN film formed through the first sequence or the second sequence ofthe embodiment is used as an insulating film, uniform performance in asurface of the SiOCN film can be provided, and contribution toimprovement in performance and yield of the semiconductor device becomespossible.

Furthermore, according to the embodiment, as the processing conditionssuch as a pressure or gas supply time in the processing chamber in eachstep of each sequence are controlled, a ratio of the respectiveelements, i.e., a silicon element, an oxygen element, a carbon element,and a nitrogen element in the SiOCN film, i.e., a silicon concentration,an oxygen concentration, a carbon concentration, and a nitrogenconcentration, can be adjusted to control a composition ratio of theSiOCN film.

In addition, in the conventional CVD method, a plurality of kinds ofgases including a plurality of elements constituting a thin film to beformed are simultaneously supplied. In this case, in order to control acomposition ratio of the thin film, for example, control of a gas supplyflow rate upon gas supply can be considered. Further, in this case, evenwhen supply conditions such as a substrate temperature, a pressure inthe processing chamber, and a gas supply time upon gas supply arecontrolled, the composition ratio of the thin film cannot be controlled.

Furthermore, in the ALD method, a plurality of kinds of gases includinga plurality of elements constituting a thin film to be formed arealternately supplied. In this case, in order to control a compositionratio of the thin film to be formed, for example, control of a gassupply flow rate and a gas supply time upon supply of each gas may beconsidered. In addition, in the case of the ALD method, since supply ofthe source gas is provided for the purpose of adsorption saturation ofthe source gas onto the substrate surface, there is no need to controlthe pressure in the processing chamber. That is, the adsorptionsaturation of the source gas is realized at any pressure value as longas the adsorption saturation of the source gas occurs at a predeterminedpressure or less in which the source gas is adsorbed with respect to thereaction temperature and the pressure in the processing chamber is apredetermined pressure or less. For this reason, conventionally, when afilm is formed through the ALD method, the pressure in the processingchamber is set to a pressure according to exhaust capability of thesubstrate processing apparatus with respect to the gas supply amount.When the pressure in the processing chamber is varied, sincechemisorption of the source gas onto the substrate surface may beinhibited or may approach the CVD reaction, film forming by the ALDmethod cannot be appropriately performed. In addition, in order to forma thin film having a predetermined film thickness through the ALDmethod, since the ALD reaction (adsorption saturation and surfacereaction) is repeatedly performed, deposition may be insufficient wheneach ALD reaction is insufficiently performed until each ALD reaction issaturated, and a sufficient deposition velocity may not be obtained.Accordingly, in the case of the ALD method, it may be difficult tocontrol the composition ratio of the thin film through control of thepressure in the processing chamber.

In the embodiment, in any sequence, as the pressure in the processingchamber or the gas supply time in each step are controlled, the thinfilm composition ratio is controlled. In addition, preferably, as thepressure in the processing chamber or the pressure and gas supply timeis controlled, the thin film composition ratio may be controlled.

When the composition ratio of the thin film is controlled as thepressure in the processing chamber in each step is controlled, influenceof an error between different substrate processing apparatuses can bereduced. That is, the composition ratio of the thin film can besimilarly controlled between different substrate processing apparatusesthrough similar control. In this case, when the gas supply time in eachstep is also controlled, the composition ratio of the thin film can beprecisely adjusted, and thus, controllability of control of thecomposition ratio of the thin film can be improved. In addition, as thepressure in the processing chamber in each step is controlled,improvement in the film-forming rate and control of the compositionratio of the thin film become possible. That is, as the pressure in theprocessing chamber is controlled, for example, improvement in a growthrate of the silicon-containing layer formed in Step 1 of each sequenceand control of the composition ratio of the thin film become possible.As described above, according to the embodiment, the composition ratioof the thin film between different substrate processing apparatuses canbe similarly controlled through similar control, controllability ofcontrol of the composition ratio of the thin film can be improved, andthe film-forming rate, i.e., productivity, can be improved.

In addition, for example, in film-forming by the ALD method, as the gassupply flow rate or the gas supply time in each step is controlled, whenthe composition ratio of the thin film is controlled, influence of anerror between different substrate processing apparatuses is increased.That is, even when similar control is performed between differentsubstrate processing apparatuses, similarly, the composition ratio ofthe thin film cannot be controlled. For example, even when the gassupply flow rate and the gas supply time are set to the same flow rateand time between different substrate processing apparatuses, due to theerror between the apparatuses, the pressure in the processing chamberdoes not have the same pressure value. Accordingly, in this case, as thepressure in the processing chamber is varied at each substrateprocessing apparatus, a desired composition ratio control cannot besimilarly performed between different substrate processing apparatus. Inaddition, due to variation in the pressure in the processing chamber ateach substrate processing apparatuses, since chemisorption of the sourcegas onto the substrate surface may be inhibited or may approach the CVDreaction, film-forming by the ALD method may not be appropriatelyperformed.

Further, according to the embodiment, since the silicon oxycarbonitridefilm having a predetermined composition can be formed, control ofetching resistance, permittivity and insulating resistance becomespossible, and formation of a silicon insulating film having a lowerpermittivity, a better etching resistance and a better insulatingresistance than a silicon nitride film (a SiN film) becomes possible.

Furthermore, in Steps 2, 3 and 5 of the first sequence and the secondsequence of the embodiment, C₃H₆ gas, NH₃ gas and O₂ gas supplied intothe processing chamber 201 are activated with heat to be supplied intothe wafer 200. Accordingly, since the reaction can be softly generated,formation, nitridation processing and oxidation processing of thecarbon-containing layer can be easily performed with controllability.

In addition, as the silicon insulating film formed by the method of theembodiment is used as a sidewall spacer, a device forming techniquehaving a small leakage current and good workability can be provided.

Further, as the silicon insulating film formed by the method of theembodiment is used as an etch stopper, a device forming technique havinggood workability can be provided.

Furthermore, according to the embodiment, a silicon insulating filmhaving an ideal stoichiometric proportion can be formed without use ofplasma. In addition, since the silicon insulating film can be formedwithout use of plasma, for example, an application to a process, inwhich plasma damage may occur, for example, an SADP film of DPT, becomespossible.

Another Embodiment of the Invention

While the embodiment of the present invention has been described indetail above, the present invention is not limited to theabove-mentioned embodiment but may be variously modified withoutdeparting from the spirit of the present invention.

For example, O₂ gas may be directly supplied into the processing chamber201 through the fourth nozzle 249 d, rather than installing the bufferchamber 237 in the processing chamber 201. In this case, the gas supplyhole 250 d of the fourth nozzle 249 d may be directed toward the centerof the reaction tube 203 to directly supply the O₂ gas toward the wafer200 through the fourth nozzle 249 d. In addition, only the bufferchamber 237 may be installed without installation of the fourth nozzle249 d.

Further, for example, C₃H₆ gas, NH₃ gas and O₂ gas supplied into theprocessing chamber 201 may be activated using, for example, plasma, notlimited to activation with heat. In this case, for example, each gas maybe plasma-excited using a plasma source, which is a plasma generator.

Furthermore, for example, in Step 5 of the first sequence and the secondsequence, a hydrogen-containing gas may be supplied with anoxygen-containing gas. As the oxygen-containing gas and thehydrogen-containing gas are supplied into the processing vessel under apressure under a heated atmospheric pressure (decompression) atmosphere,the oxygen-containing gas and the hydrogen-containing gas may be reactedwith each other in the processing vessel to generate an oxidizingspecies including oxygen such as atomic oxygen (0), and oxidation may beperformed by the oxidizing species. In this case, an oxidizing force,i.e., an oxidizing rate, can be improved in comparison with the case inwhich oxidation is performed by the oxygen-containing gas only, and anoxidation time can be reduced. The oxidation processing is performedunder a non-plasma decompression atmosphere. As the hydrogen-containinggas, for example, hydrogen (H₂) gas, ammonia (NH₃) gas, methane (CH₄)gas, and so on may be used. In this case, the hydrogen-containing gas issupplied through the hydrogen-containing gas supply system.

In addition, in the above-mentioned embodiment, while an example inwhich, after the SiCN layer is deposited on the wafer to one layer ormore, the SiO layer is deposited to one layer or more, and these arealternately repeated to form the SiOCN film through stacking has beendescribed, a sequence of the stacking may be reversed. That is, afterthe SiO layer is deposited on the wafer to one layer or more, the SiCNlayer may be deposited to one layer or more, and these may bealternately repeated to form the SiOCN film through the stacking.

Further, in the above-mentioned embodiment, while an example in which,after the SiCN layer is deposited to one layer or more, the SiO layer isdeposited to one layer or more, and these are alternately repeated toform the SiOCN film through the stacking has been described, the SiOCNfilm may be formed through the stacking of a layer different from theselayers.

For example, after the SiOC layer is deposited to one layer or more, theSiN layer may be deposited to one layer or more, and these may bealternately repeated to form the SiOCN film through the stacking. Inthis case, a process of supplying a silicon-containing gas, acarbon-containing gas, and an oxygen-containing gas into the processingvessel, in which the wafer is accommodated, to form a SiOC layer havinga predetermined thickness, and a process of supplying asilicon-containing gas and a nitrogen-containing gas into the processingvessel to form a SiN layer having a predetermined thickness arealternately repeated to form a SiOCN film having a predetermined filmthickness and formed by alternately stacking the SiOC layer and the SiNlayer on the wafer. Even in this case, a sequence of the stacking may bereversed. That is, after the SiN layer is deposited to one layer ormore, the SiOC layer may be deposited to one layer or more, and thesemay be alternately repeated to form the SiOCN film through the stacking.

In addition, for example, after the SiON layer is deposited to one layeror more, the SiC layer may be deposited to one layer or more, and thesemay be alternately repeated to form the SiOCN film through the stacking.In this case, a process of supplying a silicon-containing gas, anitrogen-containing gas and an oxygen-containing gas into the processingvessel, in which the wafer is accommodated, to form a SiON layer havinga predetermined thickness, and a process of supplying asilicon-containing gas and a carbon-containing gas into the processingvessel to form a SiC layer having a predetermined thickness arealternately repeated to form a SiOCN film having a predetermined filmthickness and formed by alternately stacking the SiON layer and the SiClayer on the wafer. In this case, a sequence of the stacking may bereversed. That is, after the SiC layer is deposited to one layer ormore, the SiON layer may be deposited to one layer or more, and thesemay be alternately repeated to form the SiOCN film through the stacking.

That is, after a layer of one layer or more including Si and at leastone of O, C and N is deposited, a layer of one layer or more includingSi and other elements, other than the at least one of O, C and N, may bedeposited, and these may be alternately repeated to form a SiOCN filmthrough the stacking. However, in comparison with the case in which theSiOC layer and the SiN layer are alternately stacked to form the SiOCNfilm or the case in which the SiON layer and the SiC layer arealternately stacked to form the SiOCN, like the embodiment, the SiOCNfilm may be formed with better controllability in the case in which theSiCN layer and the SiO layer are alternately stacked on the wafer toform the SiOCN film.

In addition, in the embodiment, while an example in which the SiCN layeris deposited to one layer or more, the SiO layer is deposited to onelayer or more, and these are alternately repeated to form the SiOCN filmthrough the stacking has been described, instead of the SiO layer, aboron nitride layer (a BN layer) may be deposited, and instead of theSiOCN film, a silicon boron carbonitride film (a SiBCN film) may beformed. That is, the film forming technique of the SiOCN film (alaminate method) in the above-mentioned embodiment may be applied to thefilm-forming of the SiBCN film. In this case, after the SiCN layer isdeposited to one layer or more, the BN layer is deposited to one layeror more, and these are alternately repeated to form the SiBCN throughthe stacking.

In this case, specifically, a process of supplying a silicon-containinggas, a carbon-containing gas, and a nitrogen-containing gas to theheated wafer 200 in the processing vessel to form a silicon carbonitridelayer (a SiCN layer) having a predetermined thickness; and a process ofsupplying a boron-containing gas and a nitrogen-containing gas to theheated wafer 200 in the processing vessel to form a boron nitride layer(a BN layer) having a predetermined thickness are alternately repeatedto form a silicon boron carbonitride film (a SiBCN film) having apredetermined thickness and formed by alternately stacking the siliconcarbonitride layer and the boron nitride layer on the wafer 200.

FIGS. 7 and 8 show a film-forming flow and gas supply timing of anexample of a sequence (hereinafter referred to as a first sequence of anapplied example) in which the film-forming according to the firstsequence of the above-mentioned embodiment is applied to film-forming ofthe SiBCN film, respectively.

In the first sequence of the applied example, a process (Step 1) ofsupplying a silicon-containing gas to the heated wafer 200 in theprocessing vessel to form a silicon-containing layer, a process (Step 2)of supplying a carbon-containing gas to the heated wafer 200 in theprocessing vessel to form a carbon-containing layer on thesilicon-containing layer to form a layer including silicon and carbon, aprocess (Step 3) of supplying a nitrogen-containing gas to the heatedwafer 200 in the processing vessel to nitride the layer includingsilicon and carbon to form a silicon carbonitride layer (a SiCN layer),a process (Step 4) of supplying a boron-containing gas to the heatedwafer 200 in the processing vessel to form a boron-containing layer, anda process (Step 5) of supplying a nitrogen-containing gas to the heatedwafer 200 in the processing vessel to nitride the boron-containing layerto form a boron nitride layer (a BN layer) are set as one cycle, and thecycle is performed a predetermined number of times (n times) to form asilicon boron carbonitride film (a SiBCN film) having a predeterminedthickness and formed by alternately stacking the silicon carbonitridelayer and the boron nitride layer on the wafer 200.

In addition, FIGS. 9 and 10 show a film-forming flow and gas supplytiming of an example of a sequence (hereinafter referred to as a secondsequence of the applied example) in which the film-forming according tothe second sequence of the above-mentioned embodiment is applied tofilm-forming of the SiBCN film, respectively.

In the second sequence of the applied example, a process in which aprocess (Step 1) of supplying a silicon-containing gas to the heatedwafer 200 in the processing vessel to form a silicon-containing layer, aprocess (Step 2) of supplying a carbon-containing gas to the heatedwafer 200 in the processing vessel to form a carbon-containing layer onthe silicon-containing layer to form a layer including silicon andcarbon, and a process (Step 3) of supplying a nitrogen-containing gas tothe heated wafer 200 in the processing vessel to nitride the layerincluding silicon and carbon to form a silicon carbonitride layer areset as a first set, and the first set is performed a predeterminednumber of times (x times) to form a silicon carbonitride layer (a SiCNlayer) having a predetermined thickness; and a process in which aprocess (Step 4) of supplying a boron-containing gas to the heated wafer200 in the processing vessel to form a boron-containing layer, and aprocess (Step 5) of supplying a nitrogen-containing gas to the heatedwafer 200 in the processing vessel to nitride the boron-containing layerto form a boron nitride layer are set as a second set, and the secondset is performed a predetermined number of times (y times) to form aboron nitride layer (a BN layer) having a predetermined thickness; areset as one cycle, and the cycle is performed a predetermined number oftimes (n times) to form a silicon boron carbonitride film (a SiBCN film)having a predetermined film thickness and formed by alternately stackingthe silicon carbonitride layer and the boron nitride layer on the wafer200.

In either of the first sequence and the second sequence of the appliedexample, the above-mentioned cycle may be repeated a plurality of times.In addition, in either of the first sequence and the second sequence ofthe applied example, in the process of forming the silicon-containinglayer, the silicon-containing gas is supplied to the wafer 200 under acondition in which a CVD reaction occurs, and in the process of formingthe boron-containing layer, the boron-containing gas is supplied to thewafer 200 under a condition in which a CVD reaction occurs.

In the first sequence and the second sequence of the applied example,for example, boron trichloride (BCl₃) gas or diborane (B₂H₆) gas may beused as the boron-containing gas. In FIGS. 7, 8, 9 and 10, an example ofusing BCl₃ gas as the boron-containing gas is shown. Theboron-containing gas is supplied through the boron-containing gas supplysystem. Processing conditions upon supply of the silicon-containing gas,the carbon-containing gas and the nitrogen-containing gas may besubstantially the same as the processing conditions upon supply of thesilicon-containing gas, the carbon-containing gas and thenitrogen-containing gas in the above-mentioned embodiment, andprocessing conditions upon supply of the boron-containing gas may besubstantially the same as the processing conditions upon supply of thecarbon-containing gas in the above-mentioned embodiment. In addition,while a chemisorption layer of a boron layer (a B layer) or aboron-containing gas (for example, BCl₃ gas), which is aboron-containing layer, i.e., a chemisorption layer of a material(BCl_(x)) decomposed from the BCl₃ gas, is formed on the SiCN layer bysupply of the boron-containing gas, even in this case, an adsorptionstate thereof may become an unsaturated state.

In addition, in order for the adsorption state of the BCl_(x) onto theSiCN layer to be unsaturated, while the processing conditions uponsupply of the boron-containing gas may be substantially the same as theabove-mentioned processing conditions, when the processing conditionsupon supply of the boron-containing gas are replaced with the followingprocessing conditions, the adsorption state of the BCl_(x) onto the SiCNlayer can be easily unsaturated.

Wafer temperature: 500 to 630° C.

Pressure in processing chamber: 133 to 2,666 Pa

BCl₃ gas partial pressure: 67 to 2,515 Pa

BCl₃ gas supply flow rate: 1,000 to 5,000 sccm

N₂ gas supply flow rate: 300 to 1,000 sccm

BCl₃ gas supply time: 6 to 100 seconds

According to the applied embodiment, operational effects similar to theabove-mentioned embodiment can be obtained. For example, in the firstsequence or the second sequence of the applied embodiment, as theprocessing conditions such as the pressure or gas supply time in theprocessing vessel of each step are controlled, a ratio of each element,i.e., a silicon element, a boron element, a carbon element and anitrogen element in the SiBCN layer, i.e., a silicon concentration, aboron concentration, a carbon concentration and a nitrogenconcentration, can be adjusted to control a composition ratio of theSiBCN film.

In addition, for example, in the first sequence or the second sequenceof the applied example, as a thickness of either of the SiCN layer andthe BN layer is controlled, a composition ratio of the SiBCN film can becontrolled. For example, when the SiCN layer having a thickness ofseveral atomic layers and the BN layer having a thickness of less thanone atomic layer are alternately stacked, a ratio of the siliconelement, the nitrogen element and the carbon element with respect to theboron element of the SiBCN film can be controlled to be enriched (aratio of the boron element becomes poor). In addition, for example, whenthe SiCN layer having a thickness of less than one atomic layer and theBN layer having a thickness of several atomic layers are alternatelystacked, a ratio of the silicon element and the boron element withrespect to the nitrogen element and the carbon element of the SiBCN filmcan be controlled to be enriched (a ratio of the nitrogen element andthe carbon element becomes poor). Further, according to the processingconditions, the SiCN layer and the BN layer, which are alternatelystacked, can be diffused to each other.

Further, for example, in the second sequence of the applied embodiment,as a layer number of at least one layer of the SiCN layer and the BNlayer, i.e., a set number (x, y) is controlled, the composition ratio ofthe SiBCN film can be precisely controlled. For example, when the SiCNlayer of five layers and the BN layer of two layers are alternatelystacked, a ratio of the silicon element, the nitrogen element and thecarbon element with respect to the boron element of the SiBCN film canbe controlled to be enriched (a ratio of the boron element becomespoor). In addition, for example, when the SiCN layer of two layers andthe BN layer of five layers are alternately stacked, a ratio of thesilicon element and the boron element with respect to the nitrogenelement and the carbon element of the SiBCN film can be controlled to beenriched (a ratio of the nitrogen element and the carbon element becomespoor). Further, according to a combination of the set number (x, y),minute composition control in which a ratio of a specific elementbecomes a small amount (for example, several %) becomes possible.Furthermore, since increase in each set number can increase the layernumber of the SiCN layer or the BN layer formed at each one cycle by theset number, improvement in cycle rate and improvement in film-formingrate become possible.

In addition, for example, while an example in which a silicon-basedinsulating film (a SiOCN film) including a semiconductor element such assilicon, which is an oxycarbonitride film, has been described in theabove-mentioned embodiment, the present invention may be applied to thecase in which a metal-based thin film including a metal element such astitanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), aluminum(Al), molybdenum (Mo), tungsten (W), gallium (Ga) and germanium (Ge) isformed.

That is, the present invention may be applied to the case in which ametal oxycarbonitride film such as a titanium oxycarbonitride film (aTiOCN film), a zirconium oxycarbonitride film (a ZrOCN film), a hafniumoxycarbonitride film (a HfOCN film), a tantalum oxycarbonitride film (aTaOCN film), an aluminum oxycarbonitride film (an AlOCN film), amolybdenum oxycarbonitride film (a MoOCN film), a tungstenoxycarbonitride film (a WOCN film), a gallium oxycarbonitride film (aGaOCN film), a germanium oxycarbonitride film (a GeOCN film), acombination thereof, or a mixture thereof is formed.

In this case, instead of the silicon source gas in the above-mentionedembodiment, film-forming may be performed by the sequence of theabove-mentioned embodiment (the first sequence and the second sequence)using a metal source gas (a metal element-containing gas) such as atitanium source gas, a zirconium source gas, a hafnium source gas, atantalum source gas, an aluminum source gas, a molybdenum source gas, atungsten source gas, a gallium source gas and a geranium source gas.

That is, in this case, for example, in the first sequence, a process(Step 1) of supplying a metal element-containing gas to the heated wafer200 in the processing vessel to form a metal element-containing layer, aprocess (Step 2) of supplying a carbon-containing gas to the heatedwafer 200 in the processing vessel to form a carbon-containing layer onthe metal element-containing layer to form a layer including a metalelement and carbon, a process (Step 3) of supplying anitrogen-containing gas to the heated wafer 200 in the processing vesselto nitride the layer including a metal element and carbon to form ametal carbonitride layer, a process (Step 4) of supplying a metalelement-containing gas to the heated wafer 200 in the processing vesselto form a metal element-containing layer, and a process (Step 5) ofsupplying an oxygen-containing gas to the heated wafer 200 in theprocessing vessel to oxidize the metal element-containing layer to forma metal oxide layer are set as one cycle, and the cycle is performed apredetermined number of times (n times) to form a metal oxycarbonitridefilm having a predetermined film thickness and formed by alternatelydeposing the metal carbonitride layer and the metal oxide layer on thewafer 200.

In addition, in this case, for example, in the second sequence, aprocess in which a process (Step 1) of supplying a metalelement-containing gas to the heated wafer 200 in the processing vesselto form a metal element-containing layer, a process (Step 2) ofsupplying a carbon-containing gas to the heated wafer 200 in theprocessing vessel to form a carbon-containing layer on the metalelement-containing layer to form a layer including a metal element andcarbon, and a process (Step 3) of supplying a nitrogen-containing gas tothe heated wafer 200 in the processing vessel to nitride the layerincluding a metal element and carbon to form a metal carbonitride layerare set as a first set, and the first set is performed a predeterminednumber of times (x times) to form the metal carbonitride layer having apredetermined thickness; and a process in which a process (Step 4) ofsupplying a metal element-containing gas to the heated wafer 200 in theprocessing vessel to form a metal element-containing layer, and aprocess (Step 5) of supplying an oxygen-containing gas to the heatedwafer 200 in the processing vessel to oxidize the metalelement-containing layer to form a metal oxide layer are set as a secondset, and the second set is performed a predetermined number of times (ytimes) to form the metal oxide layer having a predetermined thickness;are set as one cycle, and the cycle is performed a predetermined numberof times (n times) to form a metal oxycarbonitride film having apredetermined film thickness and formed by alternately stacking themetal carbonitride layer and the metal oxide layer on the wafer 200.

In either of the first sequence and the second sequence, theabove-mentioned cycle may be repeated a plurality of times. In addition,in either of the first sequence and the second sequence, in the processof forming the metal element-containing layer, the metalelement-containing gas is supplied to the wafer 200 under a condition inwhich a CVD reaction occurs.

For example, when a TiOCN film is formed as the metal oxycarbonitridefilm, an organic source such as tetrakisethylmethylaminotitanium(Ti[N(C₂H₅)(CH₃)]₄, abbreviation: TEMAT), tetrakisdimethlyaminotitanium(Ti[N(CH₃)₂]₄, abbreviation: TDMAT), and tetrakisdiethylaminotitanium(Ti[N(C₂H₅)₂]₄, abbreviation: TDEAT), or an inorganic source such astitanium tetrachloride (TiCl₄) may be used as a source including Ti. Thegases of the above-mentioned embodiment may be used as thecarbon-containing gas, the nitrogen-containing gas, or theoxygen-containing gas. In addition, while the processing conditions atthis time may be the same processing conditions as in theabove-mentioned embodiment, more preferably, a wafer temperature may bewithin a range of, for example, 100 to 500° C., and a pressure in theprocessing chamber may be within a range of, for example, 1 to 1,000 Pa.

In addition, for example, when a ZrOCN film is formed as the metaloxycarbonitride film, an organic source such astetrakisethylmethylaminozirconium (Zr[N(C₂H₅)(CH₃)]₄, abbreviation:TEMAZ), tetrakisdimethylaminozirconium (Zr[N(CH3)₂]₄, abbreviation:TDMAZ), and tetrakisdiethylaminozirconium (Zr[N(C₂H₅)₂]₄, abbreviation:TDEAZ), or an inorganic source such as zirconium tetrachloride (ZrCl₄)may be used as a source including Zr. The gases in the above-mentionedembodiment may be used as the carbon-containing gas, thenitrogen-containing gas, or the oxygen-containing gas. In addition,while the processing conditions at this time may be the same processingconditions as in the above-mentioned embodiment, more preferably, awafer temperature may be within a range of, for example, 100 to 400° C.,and a pressure in the processing chamber may be within a range of, forexample, 1 to 1,000 Pa.

Further, for example, when a HfOCN film is formed as the metaloxycarbonitride film, an organic source such astetrakisethylmethylaminohafnium (Hf[N(C₂H₅)(CH₃)]₄, abbreviation:TEMAH), tetrakisdimethylamonohafnium (Hf[N(CH₃)₂]₄, abbreviation:TDMAH), and tetrakisdiethylaminohafnium (Hf[N(C₂H₅)₂]₄, abbreviation:TDEAH), or an inorganic source such as hafnium tetrachloride (HfCl₄) maybe used as a source including Hf. The gases in the above-mentionedembodiment may be used as the carbon-containing gas, thenitrogen-containing gas, or the oxygen-containing gas. In addition,while the processing conditions at this time may be the same processingconditions as in the above-mentioned embodiment, more preferably, awafer temperature may be within a range of, for example, 100 to 400° C.,and a pressure in the processing chamber may be within a range of, 1 to1,000 Pa.

Furthermore, for example, when a TaOCN film is formed as the metaloxycarbonitride film, an organic source such as pentaethoxytantalum(Ta(O₂CH₅)₅, abbreviation: PET), andtrisdiethylaminotertiarybutyliminotantalum (Ta(NC(CH₃)₃)(N(C₂H₅)₂)₃,abbreviation: TBTDET), or an inorganic source such as tantalumpentachloride (TaCl₅) and tantalum pentafluoride (TaF₅) may be used as asource including Ta. The gases in the above-mentioned embodiment may besued as the carbon-containing gas, the nitrogen-containing gas, or theoxygen-containing gas. In addition, while the processing conditions atthis time may be the same processing conditions as in theabove-mentioned embodiment, more preferably, a wafer temperature may bewithin a range of, for example, 100 to 500° C., and a pressure in theprocessing chamber may be within a range of, 1 to 1,000 Pa.

Further, for example, when an AlOCN film is used as the metaloxycarbonitride film, an organic source such as trimethylaluminum(Al(CH₃)₃, abbreviation: TMA) or an inorganic source such astrichloroaluminum (AlCl₃) may be used as a source including Al. Thegases in the above-mentioned embodiment may be used as thecarbon-containing gas, the nitrogen-containing gas, or theoxygen-containing gas. In addition, while the processing conditions atthis time may be the same processing conditions as in theabove-mentioned embodiment, more preferably, a wafer temperature may bewithin a range of, for example, 100 to 400° C., and a pressure in theprocessing chamber may be within a range of, 1 to 1,000 Pa.

As described above, the present invention may be applied to thefilm-forming of the metal oxycarbonitride film, and even in this case,operational effects similar to the above-mentioned embodiment may beprovided. That is, the present invention may be applied to the case inwhich an oxycarbonitride film including a predetermined element such asa semiconductor element or a metal element is formed.

In addition, while an example in which the film-forming is performedusing a batch-type substrate processing apparatus configured to processa plurality of substrates at a time has been described in theabove-mentioned embodiment, the present invention is not limited theretobut may be applied to the case in which the film-forming is performedusing a sheet-feeding type substrate processing apparatus configured toprocess one or a plurality of substrates at a time.

Further, each of the above-mentioned embodiment, variant and appliedexample may be appropriately combined and used.

Furthermore, the present invention may be realized even when, forexample, the process recipe of the conventional substrate processingapparatus is varied. When the process recipe is varied, the processrecipe in accordance with the present invention may be installed in theconventional substrate processing apparatus via an electriccommunication line or a recording medium in which the process recipe isrecorded, or an input/output device of the conventional substrateprocessing apparatus may be operated to change the process recipe itselfinto the process recipe in accordance with the present invention.

EXAMPLE First Example

A SiOCN film was formed while controlling a composition ratio by thefirst sequence according to the embodiment, and a composition ratio ofthe SiOCN film and film thickness uniformity in a wafer surface weremeasured. HCD gas, which is a silicon-containing gas, C₃H₆ gas, which isa carbon-containing gas, NH₃ gas, which is a nitrogen-containing gas,and O₂ gas, which is an oxygen-containing gas, were used. Control of thecomposition ratio of the SiOCN film was performed by adjusting apressure and gas supply time (irradiation time), which are parametersfor controlling the composition ratio.

First, the pressure in the processing chamber in a second step of thefirst sequence and C₃H₆ gas supply time of the second step wereadjusted, and the SiOCN film having a carbon concentration of about 8atoms % was framed on a wafer. The processing conditions at this timewere set as the following conditions.

<First Sequence (Standard Processing Conditions)>

(First Step)

Temperature in processing chamber: 630° C.

Pressure in processing chamber: 133 Pa (1 Torr)

HCD gas supply flow rate: 0.2 slm

HCD gas irradiation time: 6 seconds

(Second Step)

Temperature in processing chamber: 630° C.

Pressure in processing chamber: 399 Pa (3 Torr)

C₃H₆ gas supply flow rate: 1 slm

C₃H₆ gas irradiation time: 12 seconds

(Third Step)

Temperature in processing chamber: 630° C.

Pressure in processing chamber: 866 Pa (6.5 Torr)

NH₃ gas supply flow rate: 4.5 slm

NH₃ gas irradiation time: 18 seconds

(Fourth Step)

Temperature in processing chamber: 630° C.

Pressure in processing chamber: 133 Pa (1 Torr)

HCD gas supply flow rate: 0.2 slm

HCD gas irradiation time: 6 seconds

(Fifth Step)

Temperature in processing chamber: 630° C.

Pressure in processing chamber: 133 Pa (1 Torr)

O₂ gas supply flow rate: 1 slm

O₂ gas irradiation time: 18 seconds

As the processing conditions were set as standard processing conditionsand the processing conditions were adjusted, formation of the SiOCN filmhaving a carbon concentration of about 12 atoms % was tested.

As a result, as the pressure in the processing chamber in the secondstep was set from 399 Pa (3 Torr) to 2394 Pa (18 Torr), the SiOCN filmhaving a carbon concentration of about 12 atoms % was obtained and theSiOCN film having a carbon ratio higher than that of the SiOCN filmformed by the standard processing conditions could be obtained. That is,as the pressure in the processing chamber in the second step was set tobe higher than the pressure in the processing chamber in the standardprocessing conditions, the SiOCN film having a high carbon ratio couldbe formed. In addition, the nitrogen concentration was reduced by anincrease in carbon concentration. In addition, processing conditionsother than the pressure in the processing chamber in the second stepwere set the same as the standard processing conditions. That is, theprocessing conditions at this time were set as the following conditions.

<First Sequence (Pressure Change Upon Supply of C₃H₆ Gas)>

(First Step)

Temperature in processing chamber: 630° C.

Pressure in processing chamber: 133 Pa (1 Torr)

HCD gas supply flow rate: 0.2 slm

HCD gas irradiation time: 6 seconds

(Second Step)

Temperature in processing chamber: 630° C.

Pressure in processing chamber: 2,394 Pa (18 Torr)

C₃H₆ gas supply flow rate: 1 slm

C₃H₆ gas irradiation time: 12 seconds

(Third Step)

Temperature in processing chamber: 630° C.

Pressure in processing chamber: 866 Pa (6.5 Torr)

NH₃ gas supply flow rate: 4.5 slm

NH₃ gas irradiation time: 18 seconds

(Fourth Step)

Temperature in processing chamber: 630° C.

Pressure in processing chamber: 133 Pa (1 Torr)

HCD gas supply flow rate: 0.2 slm

HCD gas irradiation time: 6 seconds

(Fifth Step)

Temperature in processing chamber: 630° C.

Pressure in processing chamber: 133 Pa (1 Torr)

O₂ gas supply flow rate: 1 slm

O₂ gas irradiation time: 18 seconds

In addition, as a C₃H₆ gas irradiation time in the second step was setfrom 12 seconds to 72 seconds, the SiOCN film having a carbonconcentration of about 12 atoms % was obtained, and a SiOCN film havinga carbon ratio higher than that of the SiOCN film formed by the standardprocessing conditions could be formed. That is, the C₃H₆ gas irradiationtime in the second step was set to be larger than the C₃H₆ gasirradiation time in the standard processing conditions, and the SiOCNfilm having a high carbon ratio could be formed. In addition, thenitrogen concentration was reduced by an increase in carbonconcentration. Further, the processing conditions other than the C₃H₆gas irradiation time in the second step were set the same as thestandard processing conditions. That is, the processing conditions atthis time were set as the following conditions.

<First Sequence (C₃H₆ Gas Irradiation Time Change)>

(First Step)

Temperature in processing chamber: 630° C.

Pressure in processing chamber: 133 Pa (1 Torr)

HCD gas supply flow rate: 0.2 slm

HCD gas irradiation time: 6 seconds

(Second Step)

Temperature in processing chamber: 630° C.

Pressure in processing chamber: 399 Pa (3 Torr)

C₃H₆ gas supply flow rate: 1 slm

C₃H₆ gas irradiation time: 72 seconds

(Third Step)

Temperature in processing chamber: 630° C.

Pressure in processing chamber: 866 Pa (6.5 Torr)

NH₃ gas supply flow rate: 4.5 slm

NH₃ gas irradiation time: 18 seconds

(Fourth Step)

Temperature in processing chamber: 630° C.

Pressure in processing chamber: 133 Pa (1 Torr)

HCD gas supply flow rate: 0.2 slm

HCD gas irradiation time: 6 seconds

(Fifth Step)

Temperature in processing chamber: 630° C.

Pressure in processing chamber: 133 Pa (1 Torr)

O₂ gas supply flow rate: 1 slm

O₂ gas irradiation time: 18 seconds

At this time, since the film thickness uniformity in the wafer surfaceof each formed SiOCN film was within a range of ±1.5%, good results wereobtained. In addition, it will be appreciated that the film thicknessuniformity in the wafer surface shows a degree of deviation in filmthickness distribution in the wafer surface, and as the degree isreduced, film thickness distribution uniformity in the wafer surface isimproved.

As described above, according to the example, it will be appreciatedthat the SiOCN film having good film thickness uniformity in the wafersurface can be formed. In addition, it will be appreciated that, whenthe SiOCN film according to the example is used as an insulating film,uniform performance in the surface of the SiOCN film can be provided,and can contribute to improvement in performance of the semiconductordevice or improvement in yield.

Second Example

A SiOCN film was formed while controlling a composition ratio by thesecond sequence of the above-mentioned embodiment, and the compositionratio of the SiOCN film and film thickness uniformity in the wafersurface were measured. HCD gas, which is a silicon-containing gas, C₃H₆gas, which is a carbon-containing gas, NH₃ gas, which is anitrogen-containing gas, and O₂ gas, which is an oxygen-containing gas,were used. The processing conditions in each step were set to the sameprocessing conditions as each step of the standard processing conditionsof the first example. Control of the composition ratio of the SiOCN filmwas performed by adjusting each set number in the second sequence, i.e.,a set number (x) of a SiCN layer forming process and a set number (y) ofa SiO layer forming process.

As a result, when the set number (x) of the SiCN layer forming processin the second sequence was set to 2 and the set number (y) of the SiOlayer forming process was set to 1 (x=2, y=1), the SiOCN film having acarbon concentration of about 16 atoms was obtained and the SiOCN filmhaving a carbon ratio higher than that of the SiOCN film formed by thefirst example, i.e., the first sequence (standard processing conditions)could be formed. In addition, the case (x=1, y=1) in which the setnumber (x) of the SiCN layer forming process is set to 1 and the setnumber (y) of the SiO layer forming process was set to 1 corresponds tothe first sequence. That is, as the set number (x) of the SiCN layerforming process in the second sequence was set to be larger than aperformance number (one time) per cycle of the SiCN layer formingprocess in the first sequence, the SiOCN film having a high carbon ratiocould be formed. In addition, the nitrogen concentration was reduced byan increase in carbon concentration. Here, film thickness uniformity inthe wafer surface of the SiOCN film was within a range of ±1.5% and agood result was obtained.

As described above, according to the example, the SiOCN film having goodfilm thickness uniformity in the wafer surface could be obtained. Inaddition, when the SiOCN film according to the example was used as aninsulating film, uniform performance in the surface of the SiOCN filmcould be provided, and could contribute to improvement in performance ofthe semiconductor device or improvement in yield.

EXEMPLARY EMBODIMENT OF THE INVENTION

Hereinafter, exemplary embodiments of the present invention will beadditionally stated.

(Supplementary Note 1)

According to one aspect of the present invention, there is provided amethod of manufacturing a semiconductor device, including: (a) supplyinga gas containing an element, a carbon-containing gas and anitrogen-containing gas to a heated substrate in a processing vessel toform a carbonitride layer including the element; (b) supplying the gascontaining the element and an oxygen-containing gas to the heatedsubstrate in the processing vessel to form an oxide layer including theelement; and (c) alternately repeating the steps (a) and (b) to form onthe substrate an oxycarbonitride film having the carbonitride layer andthe oxide layer alternately stacked therein.

(Supplementary Note 2)

The method of manufacturing the semiconductor device according toSupplementary Note 1, wherein step (a) includes performing a first setof processes including supplying the gas containing the element to thesubstrate, supplying the carbon-containing gas to the substrate andsupplying the nitrogen-containing gas to the substrate a predeterminednumber of times, and step (b) includes performing a second set ofprocesses including supplying the gas containing the element to thesubstrate and supplying the oxygen-containing gas to the substrate apredetermined number of times.

(Supplementary Note 3)

The method of manufacturing the semiconductor device according toSupplementary Note 1, wherein step (a) includes performing a first setof processes including supplying the gas containing the element to thesubstrate to form a first element-containing layer including theelement, supplying the carbon-containing gas to the substrate to form acarbon-containing layer on the first element-containing layer to form alayer including the element and carbon, and supplying thenitrogen-containing gas to the substrate to nitride the layer includingthe element and carbon a predetermined number of times to form thecarbonitride layer including the element, and step (b) includesperforming a second set of processes including supplying the gascontaining the element to the substrate to form a secondelement-containing layer including the element, and supplying theoxygen-containing gas to the substrate to oxidize the secondelement-containing layer a predetermined number of times to form theoxide layer including the element.

(Supplementary Note 4)

The method of manufacturing the semiconductor device according toSupplementary Note 3, wherein each of the first element-containing layerand the second element-containing layer includes at least one layer of acontinuous deposition layer of the element, a discontinuous depositionlayer of the element, a continuous chemisorption layer of the gascontaining the element, and a discontinuous chemisorption layer of thegas containing the element.

(Supplementary Note 5)

The method of manufacturing the semiconductor device according toSupplementary Note 3, wherein each of the first element-containing layerand the second element-containing layer includes at least one layer of acontinuous deposition layer of the element and a discontinuousdeposition layer of the element.

(Supplementary Note 6)

The method of manufacturing the semiconductor device according to anyone of Supplementary Notes 3 to 5, wherein the carbon-containing layerincludes a discontinuous chemisorption layer of the carbon-containinggas.

(Supplementary Note 7)

The method of manufacturing the semiconductor device according to anyone of Supplementary Notes 3 to 6, wherein step (a) includes thermallynitriding the layer including the element and carbon under a conditionwhere a nitridation reaction by the nitrogen-containing gas in the layerincluding the element and carbon is unsaturated.

(Supplementary Note 8)

The method of manufacturing the semiconductor device according to anyone of Supplementary Notes 3 to 6, wherein step (b) includes thermallyoxidizing the second element-containing layer under a condition where anoxidation reaction by the oxygen-containing gas in the secondelement-containing layer is unsaturated.

(Supplementary Note 9)

The method of manufacturing the semiconductor device according to anyone of Supplementary Notes 3 to 8, wherein each of forming the firstelement-containing layer and forming the second element-containing layerincludes supplying the gas containing the element to the substrate undera condition where a CVD reaction occurs.

(Supplementary Note 10)

The method of manufacturing the semiconductor device according to anyone of Supplementary Notes 1 to 9, wherein the element includes asemiconductor element or a metal element.

(Supplementary Note 11)

The method of manufacturing the semiconductor device according to anyone of Supplementary Notes 1 to 10, wherein the element includessilicon.

(Supplementary Note 12)

According to another aspect of the present invention, there is provideda method of manufacturing a semiconductor device, including: (a)performing a first set of processes including supplying a gas containingan element, supplying a carbon-containing gas, and supplying anitrogen-containing gas to a heated substrate in a processing vessel apredetermined number of times to form a carbonitride including theelement; (b) performing a second set of processes including supplyingthe gas containing the element to the heated substrate in the processingvessel and supplying an oxygen-containing gas to the heated substrate inthe processing vessel a predetermined number of times to form an oxidelayer including the element; and (c) alternately repeating steps (a) and(b) to form on the substrate an oxycarbonitride film having thecarbonitride layer and the oxide layer alternately stacked therein.

(Supplementary Note 13)

According to still another aspect of the present invention, there isprovided a method of manufacturing a semiconductor device, including:(a) performing a process of supplying a gas containing an element, aprocess of supplying a carbon-containing gas, and a process of supplyinga nitrogen-containing gas to a heated substrate in a processing vesselto form a carbonitride layer including the element; (b) performing aprocess of supplying the gas containing the element and a process ofsupplying an oxygen-containing gas to the heated substrate in theprocessing vessel to form an oxide layer including the element; and (c)alternately repeating steps (a) and (b) to form on the substrate anoxycarbonitride film having the carbonitride layer and the oxide layeralternately stacked therein.

(Supplementary Note 14)

According to yet another aspect of the present invention, there isprovided a method of manufacturing a semiconductor device, including:(a) pertaining a first set of processes including supplying a gascontaining an element to a heated substrate in a processing vessel toform a first element-containing layer including the element, supplying acarbon-containing gas to the heated substrate in the processing vesselto form a carbon-containing layer on the first element-containing layerto form a layer including the element and carbon, and supplying anitrogen-containing gas to the heated substrate in the processing vesselto nitride the layer including the element and carbon to form acarbonitride layer including the element a predetermined number of timesto form a carbonitride layer including the element; (b) performing asecond set of processes including supplying the gas containing theelement to the heated substrate in the processing vessel to form asecond element-containing layer including the element and supplying anoxygen-containing gas to the substrate to oxidize the secondelement-containing layer to form an oxide layer including the element apredetermined number of times to form an oxide layer including theelement; and (c) alternately repeating steps (a) and (b) to form on thesubstrate an oxycarbonitride film having the carbonitride layer and theoxide layer alternately stacked therein.

(Supplementary Note 15)

According to yet another aspect of the present invention, there isprovided a method of manufacturing a semiconductor device, including:(a) performing a process of supplying a gas containing an element to aheated substrate in a processing vessel to form a firstelement-containing layer including the element, a process of supplying acarbon-containing gas to the heated substrate in the processing vesselto form a carbon-containing layer on the first element-containing layerto form a layer including the element and carbon, and a process ofsupplying a nitrogen-containing gas to the heated substrate in theprocessing vessel to nitride the layer including the element and carbonto form a carbonitride layer including the element; and (b) performing aprocess of supplying the gas containing the element to the heatedsubstrate in the processing vessel to form a second element-containinglayer including the element and a process of supplying anoxygen-containing gas to the heated substrate in the processing vesselto oxidize the second element-containing layer to form an oxide layerincluding the element; and (c) alternately repeating steps (a) and (b)to form on the substrate an oxycarbonitride film having the carbonitridelayer and the oxide layer alternately stacked therein.

(Supplementary Note 16)

According to yet another embodiment of the present invention, there isprovided a method of processing a substrate, including: (a) performing aprocess of supplying a gas containing an element, a process of supplyinga carbon-containing gas and a process of supplying a nitrogen-containinggas to a heated substrate in a processing vessel to form a carbonitridelayer including the element; (b) performing a process of supplying thegas containing the element to the heated substrate in the processingvessel and a process of supplying an oxygen-containing gas to the heatedsubstrate in the processing vessel to form an oxide layer including theelement; and (c) alternately repeating steps (a) and (b) to form on thesubstrate an oxycarbonitride film having the carbonitride layer and theoxide layer alternately stacked therein.

(Supplementary Note 17)

According to yet another aspect of the present invention, there isprovided a substrate processing apparatus including: a processing vesselconfigured to accommodate a substrate; a heater configured to heat thesubstrate in the processing vessel; an element-containing gas supplysystem configured to supply a gas containing an element to the substratein the processing vessel; a carbon-containing gas supply systemconfigured to supply a carbon-containing gas to the substrate in theprocessing vessel; a nitrogen-containing gas supply system configured tosupply a nitrogen-containing gas to the substrate in the processingvessel; an oxygen-containing gas supply system configured to supply anoxygen-containing gas to the substrate in the processing vessel; and acontrol unit configured to control the heater, the element-containinggas supply system, the carbon-containing gas supply system, thenitrogen-containing gas supply system and the oxygen-containing gassupply system to perform (a) supplying the gas containing the element,the carbon-containing gas and the nitrogen-containing gas to the heatedsubstrate in the processing vessel to form a carbonitride layerincluding the element, (b) supplying the gas containing the element andthe oxygen-containing gas to the heated substrate in the processingvessel to form an oxide layer including the element, and (c) alternatelyrepeating (a) and (b) to form on the substrate an oxycarbonitride filmhaving the carbonitride layer and the oxide layer alternately stackedtherein.

(Supplementary Note 18)

According to yet another aspect of the present invention, there isprovided a program for causing a computer to execute: sequence (a) ofsupplying a gas containing an element, a carbon-containing gas and anitrogen-containing gas to a heated substrate in a processing vessel ofa substrate processing apparatus to form a carbonitride layer includingthe element; sequence (b) of supplying the gas containing the elementand an oxygen-containing gas to the heated substrate in the processingvessel to form an oxide layer including the element; and sequence (c) ofalternately repeating sequence (a) and sequence (b) to form on thesubstrate an oxycarbonitride film having the carbonitride layer and theoxide layer alternately stacked therein.

(Supplementary Note 19)

According to yet another aspect of the present invention, there isprovided a computer-readable recording medium storing a program forcausing a computer to execute: sequence (a) of supplying a gascontaining an element, a carbon-containing gas and a nitrogen-containinggas to a heated substrate in a processing vessel of a substrateprocessing apparatus to form a carbonitride layer including the element;sequence (b) of supplying the gas containing the element and anoxygen-containing gas to the heated substrate in the processing vesselto form an oxide layer including the element; and sequence (c) ofalternately repeating sequence (a) and sequence (b) to form on thesubstrate an oxycarbonitride film having the carbonitride layer and theoxide layer alternately stacked therein.

(Supplementary Note 20)

According to yet another aspect of the present invention, there isprovided a method of manufacturing a semiconductor device, including:(a) supplying a gas containing an element, a carbon-containing gas and anitrogen-containing gas to a heated substrate in a processing vessel toform a carbonitride layer including the element; (b) supplying aboron-containing gas and a nitrogen-containing gas to the heatedsubstrate in the processing vessel to form a boron nitride layer; and(c) alternately repeating steps (a) and (b) to form on the substrate aboron carbonitride film having the carbonitride layer and the boronnitride layer alternately stacked therein.

(Supplementary Note 21)

According to yet another aspect of the present invention, there isprovided a method of manufacturing a semiconductor device, including:(a) performing a first set of processes including supplying a gascontaining an element, supplying a carbon-containing gas and a processof supplying a nitrogen-containing gas to a heated substrate in aprocessing vessel a predetermined number of times to form a carbonitridelayer including the element; (b) performing a second set of processesincluding supplying a boron-containing gas to the heated substrate inthe processing vessel and supplying a nitrogen-containing gas to theheated substrate in the processing vessel a predetermined number oftimes to form a boron nitride layer; and (c) alternately repeating steps(a) and (b) to form on the substrate a boron carbonitride film havingthe carbonitride layer and the boron nitride layer alternately stackedtherein.

(Supplementary Note 22)

According to yet another aspect of the present invention, there isprovided a method of manufacturing a semiconductor device, including:(a) performing a process of supplying a gas containing an element, aprocess of supplying a carbon-containing gas and a process of supplyinga nitrogen-containing gas to a heated substrate in a processing vesselto form a carbonitride layer including the element; (b) performing aprocess of supplying a boron-containing gas to the heated substrate inthe processing vessel and a process of supplying a nitrogen-containinggas to the heated substrate in the processing vessel to form a boronnitride layer; and (c) alternately repeating steps (a) and (b) to formon the substrate a boron carbonitride film having the carbonitride layerand the boron nitride layer alternately stacked therein.

(Supplementary Note 23)

According to yet another aspect of the present invention, there isprovided a method of manufacturing a semiconductor device, including:(a) performing a first set of processes including supplying a gascontaining an element to a heated substrate in a processing vessel toform an element-containing layer including the element, supplying acarbon-containing gas to the heated substrate in the processing vesselto form a carbon-containing layer on the element-containing layer toform a layer including the element and carbon, and supplying anitrogen-containing gas to the heated substrate in the processing vesselto nitride the layer including the element and carbon to form acarbonitride layer including the element a predetermined number of timesto form a carbonitride layer including the element; (b) performing asecond set of processes including supplying a boron-containing gas tothe heated substrate in the processing vessel to form a boron-containinglayer and supplying the nitrogen-containing gas to the heated substratein the processing vessel to nitride the boron-containing layer to form aboron nitride layer a predetermined number of times to form a boronnitride layer; and (c) alternately repeating steps (a) and (b) to formon the substrate a boron carbonitride film having the carbonitride layerand the boron nitride layer alternately stacked therein.

(Supplementary Note 24)

According to yet another aspect of the present invention, there isprovided a method of manufacturing a semiconductor device, including:(a) performing a process of supplying a gas containing an element to aheated substrate in a processing vessel to form an element-containinglayer including the element, a process of supplying a carbon-containinggas to the heated substrate in the processing vessel to form acarbon-containing layer on the element-containing layer to form a layerincluding the element and carbon, and a process of supplying anitrogen-containing gas to the heated substrate in the processing vesselto nitride the layer including the element and carbon to form acarbonitride layer including the element, (b) performing a process ofsupplying a boron-containing gas to the heated substrate in theprocessing vessel to form a boron-containing layer and a process ofsupplying the nitrogen-containing gas to the heated substrate in theprocessing vessel to nitride the boron-containing layer to form a boronnitride layer; and (c) alternately repeating steps (a) and (b) to formon the substrate a boron carbonitride film having the carbonitride layerand the boron nitride layer alternately stacked therein.

(Supplementary Note 25)

According to yet another aspect of the present invention, there isprovided a method of processing a substrate, including: (a) supplying agas containing an element, a carbon-containing gas and anitrogen-containing gas to a heated substrate in a processing vessel toform a carbonitride layer including the element; (b) supplying aboron-containing gas and a nitrogen-containing gas to the heatedsubstrate in the processing vessel to form a boron nitride layer; and(c) alternately repeating steps (a) and (b) to form on the substrate aboron carbonitride film having the carbonitride layer and the boronnitride layer alternately stacked therein.

(Supplementary Note 26)

According to yet another aspect of the present invention, there isprovided a substrate processing apparatus including: a processing vesselconfigured to accommodate a substrate; a heater configured to heat thesubstrate in the processing vessel; an element-containing gas supplysystem configured to supply a gas containing an element to the substratein the processing vessel; a carbon-containing gas supply systemconfigured to supply a carbon-containing gas to the substrate in theprocessing vessel; a nitrogen-containing gas supply system configured tosupply a nitrogen-containing gas to the substrate in the processingvessel; a boron-containing gas supply system configured to supply aboron-containing gas to the substrate in the processing vessel; and acontrol unit configured to control the heater, the element-containinggas supply system, the carbon-containing gas supply system, thenitrogen-containing gas supply system and the boron-containing gassupply system to perform (a) supplying the gas containing the element,the carbon-containing gas and the nitrogen-containing gas to the heatedsubstrate in the processing vessel to form a carbonitride layerincluding the element, (b) supplying the boron-containing gas and thenitrogen-containing gas to the heated substrate in the processing vesselto form a boron nitride layer, and (c) alternately repeating (a) and (b)to form on the substrate a boron carbonitride film having thecarbonitride layer and the boron nitride layer alternately stackedtherein.

(Supplementary Note 27)

According to yet another aspect of the present invention, there isprovided a program for causing a computer to execute: sequence (a) ofsupplying a gas containing an element, a carbon-containing gas and anitrogen-containing gas to a heated substrate in a processing vessel ofa substrate processing apparatus to form a carbonitride layer includingthe element; sequence (b) of supplying a boron-containing gas and anitrogen-containing gas to the heated substrate in the processing vesselto form a boron nitride layer; and sequence (c) of alternately repeatingsequence (a) and sequence (b) to form on the substrate a boroncarbonitride film having the carbonitride layer and the boron nitridelayer alternately stacked therein.

(Supplementary Note 28)

According to yet another aspect of the present invention, there isprovided a computer-readable recording medium storing a program forcausing a computer to execute: sequence (a) of supplying a gascontaining an element, a carbon-containing gas and a nitrogen-containinggas to a heated substrate in a processing vessel of a substrateprocessing apparatus to form a carbonitride layer including the element;sequence (b) of supplying a boron-containing gas and anitrogen-containing gas to the heated substrate in the processing vesselto form a boron nitride layer; and sequence (c) of alternately repeatingsequence (a) and sequence (b) to form on the substrate a boroncarbonitride film having the carbonitride layer and the boron nitridelayer alternately stacked therein.

What is claimed is:
 1. A method of manufacturing a semiconductor device,comprising: (a) forming a carbonitride layer including an element byrepeating a first set of steps a predetermined number of times, thefirst set including: supplying a gas containing the element to asubstrate to form a first element-containing layer including theelement; supplying a carbon-containing gas to the substrate to form acarbon-containing layer on the first element-containing layer to form alayer including the element and carbon; and supplying anitrogen-containing gas to the substrate to nitride the layer includingthe element and carbon; (b) forming a partially oxidized layer includingthe element by repeating a second set of steps a predetermined number oftimes, the second set including: supplying the gas containing theelement to the substrate to form a second element-containing layerincluding the element; and supplying an oxygen-containing gas to thesubstrate to partially oxidize the second element-containing layerwithout saturating an oxidation reaction of the secondelement-containing layer by the oxygen-containing gas; and (c)alternately repeating the steps (a) and (b) to form on the substrate anoxycarbonitride film having the carbonitride layer and the partiallyoxidized layer alternately stacked therein.
 2. The method according toclaim 1, wherein each of the first element-containing layer and thesecond element-containing layer comprises at least one layer of acontinuous deposition layer of the element, a discontinuous depositionlayer of the element, a continuous chemisorption layer of the gascontaining the element or a discontinuous chemisorption layer of the gascontaining the element.
 3. The method according to claim 1, wherein thecarbon-containing layer comprises a discontinuous chemisorption layer ofthe carbon-containing gas.
 4. The method according to claim 1, whereinthe layer including the element and carbon is partially nitrided in thestep (a) without saturating a nitridation reaction of the layerincluding the element and carbon by the nitrogen-containing gas.
 5. Themethod according to claim 1, wherein each of forming the firstelement-containing layer and forming the second element-containing layercomprises supplying the gas containing the element to the substrateunder a condition where a CVD reaction occurs.
 6. The method accordingto claim 1, wherein the element comprises a semiconductor element or ametal element.
 7. The method according to claim 1, wherein the elementcomprises silicon.
 8. A method of processing a substrate comprising: (a)forming a carbonitride layer including an element by repeating a firstset of steps a predetermined number of times, the first set including:supplying a gas containing the element to a substrate to form a firstelement-containing layer including the element; supplying acarbon-containing gas to the substrate to form a carbon-containing layeron the first element-containing layer to form a layer including theelement and carbon; and supplying a nitrogen-containing gas to thesubstrate to nitride the layer including the element and carbon; (b)forming a partially oxidized layer including the element by repeating asecond set of steps a predetermined number of times, the second setincluding: supplying the gas containing the element to the substrate toform a second element-containing layer including the element; andsupplying an oxygen-containing gas to the substrate to partially oxidizethe second element-containing layer without saturating an oxidationreaction of the second element-containing layer by the oxygen-containinggas; and (c) alternately repeating the steps (a) and (b) to form on thesubstrate an oxycarbonitride film having the carbonitride layer and thepartially oxidized layer alternately stacked therein.
 9. The methodaccording to claim 1, wherein a thickness of the carbonitride layerdiffers from that of the partially oxidized layer.
 10. The methodaccording to claim 1, wherein the carbonitride layer is several atomiclayers thick and the partially oxidized layer is less than one atomiclayer thick.
 11. The method according to claim 1, wherein thecarbonitride layer and the partially oxidized layer alternately stackedin the oxycarbonitride film are diffused into each other when the step(a) and the step (b) are alternately repeated.
 12. The method accordingto claim 1, wherein a number of times where the first set is performeddiffers from that of the second set.
 13. The method according to claim1, wherein the first set is repeated multiple times and the second setis performed once.
 14. A method of manufacturing a semiconductor device,comprising: (a) forming a carbonitride layer including an element byrepeating a first set of steps a predetermined number of times, thefirst set including: supplying a gas containing the element to asubstrate to form a first element-containing layer including theelement; supplying a carbon-containing gas to the substrate to form acarbon-containing layer including a discontinuous chemisorption layer ofthe carbon-containing gas on the first element-containing layer to forma layer including the element and carbon; and supplying anitrogen-containing gas to the substrate to partially nitride the layerincluding the element and carbon without saturating a nitridationreaction of the layer including the element and carbon by thenitrogen-containing gas; (b) forming a partially oxidized layerincluding the element by repeating a second set of steps a predeterminednumber of times, the second set including: supplying the gas containingthe element to the substrate to form a second element-containing layerincluding the element; and supplying an oxygen-containing gas to thesubstrate to partially oxidize the second element-containing layerwithout saturating an oxidation reaction of the secondelement-containing layer by the oxygen-containing gas; and (c)alternately repeating the steps (a) and (b) to form on the substrate anoxycarbonitride film having the carbonitride layer and the partiallyoxidized layer alternately stacked therein.